􀫺Technical Field􀫻
CROSS-REFERENCE TO RELATED APPLICATION
This application claims priority to and the benefit of Korean Patent
Application Nos. 10-2015-0105323, filed on July 5 24, 2015, and 10-2016-0092873,
filed on July 21, 2016, the disclosure of which is incorporated herein by reference in
its entirety.
Technical field
10 The present invention relates to a plasticizer composition, a resin
composition, and a method of preparing the plasticizer composition.
􀫺Background Art􀫻
Generally, in plasticizers, an alcohol reacts with a polycarboxylic acid such
15 as phthalic acid and adipic acid to form an ester corresponding thereto. In addition,
in consideration of domestic and foreign regulations of phthalate-based plasticizers
which are harmful to the human body, research on plasticizer compositions that can
replace phthalate-based plasticizers such as terephthalate-based plasticizers, adipatebased
plasticizers, other polymer-based plasticizers, and the like has been
20 continuously conducted.
Meanwhile, to manufacture products such as flooring materials, wallpaper,
sheets, interior and exterior materials for automobiles, films, electric wires, and the
like, the use of a suitable plasticizer is required in consideration of migration, volatile
loss, extension, elongation, plasticizing efficiency, and the like. According to
25 properties required according to the type of industry in such various applications, i.e.,
2
tensile strength, elongation, light resistance, migration, gelation properties, and the
like, a PVC resin is mixed with a plasticizer, a filler, a stabilizer, a viscosity reducing
agent, a dispersant, an antifoaming agent, a foaming agent, or the like.
For example, from among plasticizer compositions applicable to PVC, when
inexpensive diethylhexylterephthalate is used, plasticizing efficiency is 5 low, an
absorption rate of the plasticizer is relatively low, and light resistance and migration
are also poor.
Therefore, there is a need to develop products of a novel composition, such
as products with superior properties to diethylhexylterephthalate, and continuously
10 conduct research on the most suitable technology for the use thereof as a plasticizer
for vinyl chloride-based resins.
􀫺Disclosure􀫻
􀫺Technical Problem􀫻
15 Therefore, the inventors of the present invention continuously conducted
research on plasticizers and verified a plasticizer composition capable of enhancing
poor physical properties occurring due to structural limitations, thus completing the
present invention.
That is, an object of the present invention is to provide a plasticizer capable
20 of enhancing physical properties, such as plasticizing efficiency, migration, gelation
properties, light resistance, and the like which are required for formulation of sheets
and the like, when used as a plasticizer of a resin composition, a method of preparing
the same, and a resin composition including the plasticizer.
3
􀫺Advantageous Effects􀫻
A plasticizer composition according to an embodiment of the present
invention can provide excellent physical properties, such as high plasticizing
efficiency, high tensile strength and high elongation as well as high migration
resistance, high volatilization resistance, and the like, when 5 used in a resin
composition, and, in particular, may be suitable for use in resin products which have
high plasticizing efficiency and a high absorption rate, and the like and require
environmentally-friendly plasticizers according to the use of vegetable raw materials.
10 􀫺Description of Drawings􀫻
FIG. 1 is an image showing thermal stability test results of samples of
examples and comparative examples.
􀫺BEST MODE OF THE INVENTION􀫻
15 Examples
Hereinafter, the present invention will be described in detail with reference
to the following examples. However, the examples according to the present
invention may be changed in many different forms and should not be construed as
being limited to the embodiments set forth herein. Rather, these examples are
20 provided so that this disclosure will be thorough and complete, and will fully convey
the scope of the present invention to those of ordinary skill in the art.
Preparation Example 1: Preparation of DEHTP
498.0 g of purified terephthalic acid (TPA), 1170 g of 2-ethylhexyl alcohol
4
(2-EH) (a molar ratio of TPA: 2-EH = 1.0: 3.0), and 1.54 g (0.31 parts by weight
with respect to 100 parts by weight of TPA) of a titanium-based catalyst
(tetraisopropyl titanate (TIPT)) were added to a 3L four-neck reactor equipped with a
cooler, a condenser, a decanter, a reflux pump, a temperature controller, a stirrer, and
the like, and the temperature of the reactor was slowly raised up to about 5 out 170􀔨.
The generation of produced water started at about 170􀔨, an esterification reaction
was performed at a reaction temperature of about 220􀔨 under an atmospheric
pressure condition for about 4.5 hours while continuously introducing nitrogen gas,
and the reaction was terminated when an acid value reached 0.01.
10 After the reaction was completed, distillation extraction was performed
under reduced pressure for 0.5 hours to 4 hours to remove unreacted raw materials.
Steam extraction was performed for 0.5 hours to 3 hours under reduced pressure
using steam to remove the unreacted raw materials at a predetermined amount level
or less. A temperature of a reaction solution was cooled to about 90° C to perform
15 neutralization treatment using an alkaline solution. In addition, washing may also
be performed and thereafter, water is removed by dehydrating the reaction solution.
A filter medium was introduced into the dehydrated reaction solution and stirred for
a certain period of time, followed by filtration, thereby finally obtaining 1,326.7 g
(yield: 99.0%) of di(2-ethylhexyl)terephthalate.
20
Preparation Example 2: Preparation of DINTP
DINTP was prepared in the same manner as in Preparation Example 1
except that isononyl alcohol was used instead of using 2-ethylhexyl alcohol during
the esterification reaction.
25
5
Preparation Example 3: Preparation of DEHTP/BEHTP/DBTP
mixture (first mixture)
2,000 g of di(2-ethylhexyl)terephthalate and 340 g (17 parts by weight
based on 100 parts by weight of DEHTP) of n-butanol were added to a reactor
equipped with a stirrer, a condenser, and a decanter, and then a trans-esterifica5 tion
reaction was performed at a reaction temperature of 160°C for 2 hours under a
nitrogen atmosphere to obtain an ester-based plasticizer composition including 4.0
wt% of dibutyl terephthalate (DBTP), 35.0 wt% of butyl(2-ethylhexyl)terephthalate
(BEHTP), and 61.0 wt% of di(2-ethylhexyl)terephthalate (DEHTP).
10 The reaction product was subjected to mixed distillation to remove butanol
and 2-ethylhexyl alcohol, thereby completing the preparation of a first mixture.
Preparation Example 4: Preparation of DINTP/EHINTP/DEHTP
mixture (third mixture)
15 498.0 g of purified terephthalic acid (TPA), 975 g of 2-ethylhexyl alcohol
(2-EH) (a molar ratio of TPA: 2-EH=1.0: 2.5), 216.5 g of isononyl alcohol (INA)
(molar ratio of TPA:INA=1.0: 0.5), and 1.54 g (0.31 parts by weight with respect to
100 parts by weight of TPA) of a titanium-based catalyst (tetraisopropyl titanate
(TIPT)) were added to a 3L four-neck reactor equipped with a cooler, a condenser, a
20 decanter, a reflux pump, a temperature controller, a stirrer, and the like, and the
temperature of the reactor was slowly raised up to about 170􀔨. The generation of
produced water started at about 170􀔨, an esterification reaction was performed at a
reaction temperature of about 220􀔨 under an atmospheric pressure condition for
about 4.5 hours while continuously introducing nitrogen gas, and the reaction was
25 terminated when an acid value reached 0.01.
6
After the reaction was completed, distillation extraction was performed
under reduced pressure for 0.5 hours to 4 hours to remove unreacted raw materials.
Steam extraction was performed for 0.5 hours to 3 hours under reduced pressure
using steam to remove the unreacted raw materials at a predetermined amount level
or less. A temperature of a reaction solution was cooled to about 90° C to 5 perform
neutralization treatment using an alkaline solution. In addition, washing may also
be performed and thereafter, water is removed by dehydrating the reaction solution.
A filter medium was introduced into the dehydrated reaction solution and stirred for
a certain period of time, followed by filtration, thereby finally obtaining a third
10 mixture.
For reference, the mixture of Preparation Example 4 may also be prepared
by performing a trans-esterification reaction using isononyl alcohol, instead of using
2-ethylhexyl alcohol in Preparation Example 3.
15 Preparation Example 5: Preparation of epoxidized fatty acid butyl ester
(eFABE)
A trans-esterification reaction was performed using 500 g of epoxidized
soybean oil and 490 g of butanol as reaction raw materials, thereby finally obtaining
510 g (yield: 95%) of epoxidized butyl soyate.
20
Preparation Example 6: Preparation of epoxidized fatty acid 2-
ethylhexyl ester (eFAEHE)
584 g (yield: 95%) of epoxidized 2-ethylhexyl soyate was prepared in the
same manner as in Preparation Example 5, except that 490 g of 2-ethylhexyl alcohol
25 was used instead of 490 g of butanol.
7
Compositions of examples and comparative examples using the materials
prepared according to Preparation Examples 1 to 6 are shown in Tables 1 to 5 below.

TP-based material eFAAE material Mixing weight
ratio
Example 1-1 DEHTP eFABE 7:3
Example 1-2 DEHTP eFABE 5:5
Example 1-3 DEHTP eFAEHE 7:3
Example 1-4 DEHTP eFAEHE 5:5
Example 1-5 DEHTP eFAEHE + eFABE
(5:5)
7:3
5
TP-based material eFAAE material Mixing weight
ratio
Example 2-1 DINTP eFABE 7:3
Example 2-2 DINTP eFABE 5:5
Example 2-3 DINTP eFAEHE 7:3
Example 2-4 DINTP eFAEHE 5:5
Example 2-5 DINTP eFAEHE + eFABE
(5:5)
7:3

TP-based material eFAAE material Mixing
weight ratio
Example 3-1 DEHTP/BEHTP/DBTP eFABE 7:3
Example 3-2 DEHTP/BEHTP/DBTP eFABE 5:5
Example 3-3 DEHTP/BEHTP/DBTP eFAEHE 7:3
Example 3-4 DEHTP/BEHTP/DBTP eFAEHE 5:5
Example 3-5 DEHTP/BEHTP/DBTP eFAEHE + eFABE
(5:5)
5:5

TP-based
material
eFAAE
material
Mixing
weight ratio
Third composition
8
Example
4-1
DEHTP eFABE 7:3 ESO
(60 parts by weight)
Example
4-2
DINTP eFAEHE 7:3 ESO
(100 parts by
weight)
Example
4-3
DEHTP/BEHTP
/DBTP
eFABE 7:3 ESO
(40 parts by weight)

First composition Second
composition
Mixing weight
ratio
Comparative
Example 1
DEHTP - -
Comparative
Example 2
DINTP - -
Comparative
Example 3
DEHTP/BEHTP/DBTP - -
Comparative
Example 4
DEHTP eFAME 5:5
Comparative
Example 5
DINTP eFAME 5:5
Comparative
Example 6
DIDP eFAME 7:3
Comparative
Example 7
DOP eFAME 7:3
Comparative
Example 8
DIDP eFAINE 5:5
Comparative
Example 9
DEHTP/BEHTP/DBTP eFAINE 7:3
Comparative
Example 10
DEHTP/BEHTP/DBTP eFAINE 5:5
Experimental Example 1: Specimen preparation and performance
5 evaluation
Experimental specimens were prepared using the plasticizer compositions of
the examples and the comparative examples. With reference to ASTM D638, the
specimens were prepared by mixing 40 parts by weight of each plasticizer
9
composition and 3 parts by weight of a barium-zinc stabilizer with 100 parts by
weight of PVC in a 3L super mixer at 100􀔨 and 700 rpm for 2 minutes and 1,300
rpm for about 10 minutes, and performing roll milling on the resulting mixture at
160􀔨for 3 minutes to fabricate a 5 mm sheet.
A press operation was performed on each sheet at 180􀔨 under low-5 pressure
for 2.5 minutes, and under high-pressure for 2 minutes, and a cooling operation was
performed for 3 minutes, and then a 1 to 3 mm sheet was fabricated and prepared
into several type C dumbbell-shaped specimens. A test for evaluating the following
physical properties was conducted using each specimen.
10

Hardness Measurement
Shore (shore "A") hardness was measured at 25􀔨 using ASTM D2240.
15 Tensile Strength Measurement
A breaking point of each specimen was measured after pulling the specimen
at a cross-head speed of 200 mm/min (1T) using a test instrument, i.e., U.T.M
(manufacturer: Instron, Model name: 4466) by an ASTM D638 method. Tensile
strength was calculated as follows:
20 Tensile strength (kgf/cm2) = load value (kgf)/thickness (cm) x width (cm)
Elongation Rate Measurement
A breaking point of each specimen was measured after pulling the specimen
at a cross-head speed of 200 mm/min (1T) using the U.T.M test instrument by an
25 ASTM D638 method, and an elongation rate was calculated as follows:
10
Elongation rate (%) = length after elongation/initial length x 100
Migration Loss Measurement
Specimens having a thickness of 2 mm or more were obtained according to
KSM-3156, and a PS plate was attached to opposite surfaces of each 5 specimen and
then a load of 1 kgf/cm2 was applied thereto. The specimens were maintained in a
hot air circulating oven (80􀔨) for 72 hours, taken out thereof, and cooled at room
temperature for 4 hours. Thereafter, the PS plates were removed from the opposite
surfaces of the specimen, weights before and after being maintained in the oven were
10 measured, and migration loss was calculated using the following Equation:
Migration loss (%) = {(initial weight of specimen at room temperatureweight
of specimen after maintained in oven)/initial weight of specimen at room
temperature} x 100
15 Volatile Loss Measurement
The prepared specimens were heated at 100􀔨 for 72 hours, and then the
weights of the specimens were measured.
A volatile loss of each specimen was calculated as follows:
Volatile loss (wt%)=initial weight of specimen-(weight of specimen after
20 heated at 100􀔨 for 72 hours)/initial weight of specimen x 100
Absorption Rate Measurement
An absorption rate was evaluated by measuring the time taken to reach a
state in which after resin and ester compounds were mixed together using a planatary
25 mixer (Brabender, P600) at 77􀔨and 60 rpm, and a torque of the mixer was stabilized.
11
Thermal Stability Measurement
The prepared specimens were heated to 230􀔨 in a Mathis oven, and
combustion degrees of the specimens were measured.
5
Performance evaluation results of the specimens according to the abovedescribed
test items are shown in Tables 6 to 10 below, and heat resistance
evaluation results thereof are illustrated in FIG. 1.

Hardness
(Shore
"A")
Tensile
strength
(kg/cm2)
Elongation
rate
(%)
Migration
loss
(%)
Volatile
loss
(%)
Absorption
rate
(sec)
Example 1-1 85.6 230.2 335.6 4.12 2.77 4:57
Example 1-2 84.3 232.4 314.2 4.35 3.08 4:03
Example 1-3 86.2 247.8 325.6 4.32 2.62 6:08
Example 1-4 85.1 250.3 339.5 4.56 2.84 6:49
Example 1-5 85.8 241.5 331.8 4.18 2.68 5:11
10

Hardness
(Shore
"A")
Tensile
strength
(kg/cm2)
Elongation
rate
(%)
Migration
loss
(%)
Volatile
loss
(%)
Absorption
rate
(sec)
Example 2-1 87.9 234.4 320.0 5.33 1.74 5:35
Example 2-2 86.4 232.8 325.2 5.67 2.11 4:22
Example 2-3 88.3 253.3 309.2 5.02 1.52 7:10
Example 2-4 87.3 250.1 321.7 5.42 1.89 6:10
Example 2-5 88.1 247.9 315.4 5.24 1.58 6:15

Hardness
(Shore
"A")
Tensile
strength
(kg/cm2)
Elongation
rate
(%)
Migration
loss
(%)
Volatile
loss
(%)
Absorption
rate
(sec)
Example 3-1 83.4 232.5 352.1 2.25 3.56 4:43
Example 3-2 82.1 235.6 356.8 2.39 3.21 4:03
12
Example 3-3 84.4 250.1 360.2 2.51 3.08 5:02
Example 3-4 84.2 255.7 362.8 2.74 2.83 4:42
Example 3-5 83.0 250.2 360.9 2.44 2.91 4:21

Hardness
(Shore
"A")
Tensile
strength
(kg/cm2)
Elongation
rate
(%)
Migration
loss
(%)
Volatile
loss
(%)
Absorption
rate
(sec)
Example 4-1 85.0 252.6 359.7 3.16 1.88 5:12
Example 4-2 86.7 258.9 342.1 3.41 1.02 6:45
Example 4-3 83.8 254.1 357.8 1.78 2.52 5:10

Hardness
(Shore
"A")
Tensile
strength
(kg/cm2)
Elongation
rate
(%)
Migration
loss
(%)
Volatile
loss
(%)
Absorption
rate
(sec)
Comparative
Example 1
87.4 235.9 310.1 4.00 2.44 7:25
Comparative
Example 2
89.1 239.0 303.9 5.35 1.04 8:05
Comparative
Example 3
84.7 230.8 332.3 2.11 3.84 5:32
Comparative
Example 4
83.2 215.6 308.2 8.41 6.14 2:17
Comparative
Example 5
85.1 217.4 310.5 10.52 5.88 2:28
Comparative
Example 6
88.7 234.8 284.5 5.62 4.21 9:34
Comparative
Example 7
82.4 218.4 312.4 4.33 9.51 4:22
Comparative
Example 8
86.4 238.2 265.9 4.37 3.34 11:49
Comparative
Example 9
85.2 234.1 312.5 4.15 3.08 5:25
Comparative
Example 10
85.7 238.1 310.2 5.65 3.03 5:11
5
Referring to Tables 6 to 10, it can be confirmed that, when compared to
Comparative Examples 1 to 3 not including an epoxy-based alkyl ester compound,
which is used as an existing general-purpose product having excellent basic physical
13
properties while having problems in terms of price competitiveness, limited
applications, and the like, the specimens of the examples including the same
exhibited almost the same mechanical and physical properties as those in
Comparative Examples 1 to 3 and exhibited considerable improvement in absorption
rate and migration 5 ation loss or volatile loss.
In addition, it can be confirmed that Comparative Examples 4 to 10, using
an epoxidized methyl ester compound or epoxidized isononyl ester compound not
having 4 or 8 carbon atoms from among epoxy-based alkyl ester compounds, exhibit
considerably poor basic mechanical and physical properties as compared to the
10 examples. In particular, it can be confirmed that the plasticizer compositions of
Comparative Examples 4 to 10 have problems with being used as products due to
significantly deteriorated physical properties thereof in terms of tensile strength or
elongation rate, and in the case of Comparative Examples 4 and 5, fairly poor
migration loss properties are exhibited, in the case of Comparative Examples 4, 5,
15 and 7, fairly poor volatile loss properties are exhibited, and in the case of
Comparative Example 8, a much lower absorption rate is exhibited.
From the above-described results, it can be confirmed that, when a mixture
of a terephthalate-based material and an epoxy-based alkyl ester compound wherein
the number of carbon atoms of an alkyl is 4 or 8 is used, mechanical and physical
20 properties may be enhanced and there is a considerable improvement in migration
properties or volatile loss properties.
In addition, comparing Examples 1-1 to 1-5 with Examples 3-1 to 3.5,
Examples 3-1 to 3-5 exhibit a low hardness and a high elongation rate, from which it
can be confirmed that the plasticizer compositions of Examples 3-1 to 3-5 may be
25 suitably used for specific applications.
14
In addition, it can be confirmed that, when epoxidized oil is included as an
additional composition as in Examples 4-1 to 4-3, migration loss and volatile loss
properties are significantly enhanced without deterioration of mechanical and
physical properties.
Furthermore, referring to FIG. 1, it can be confirmed that, when 5 epoxidized
oil is additionally included, thermal stability may be enhanced, and the specimen of
Comparative Example 1 or 2 was turned into black ashes through complete
combustion, and the case of Example 1-1 not including epoxidized oil was
incompletely burned as compared to the comparative examples, while the case of
10 Example 4-1 including epoxidized oil exhibited a much lower degree of combustion
than that of the comparative examples or Example 1-1.
􀫺MODE OF THE INVENTION􀫻
Hereinafter, the present invention will be described in detail.
15 The terms or words used in the present specification and claims should not
be construed as being limited to ordinary or dictionary meanings and should be
construed as meanings and concepts consistent with the spirit of the present
invention based on a principle that an inventor can appropriately define concepts of
terms to explain the invention of the inventor in the best way.
20 The term "butyl" as used herein refers to a C4 alkyl group containing both a
straight chain and a branched chain, and examples thereof include n-butyl, isobutyl,
and t-butyl. Preferably, the butyl group may be n-butyl or isobutyl.
The terms "octyl" and "2-ethylhexyl" as used herein refers to a C8 alkyl
group, and the term "octyl" may be interchangeably used with an abbreviation for 2-
25 ethylhexyl. In some cases, the octyl group may refer to octyl as a straight alkyl
15
group, or 2-ethylhexyl as a branched alkyl group.
Plasticizer Composition
According to an embodiment of the present invention, there is provided a
plasticizer composition including: a terephthalate-based material; 5 al; and an epoxybased
alkyl ester compound, in which a weight ratio of the terephthalate-based
material to the epoxy-based alkyl ester compound is 99:1 to 1:99, and the epoxybased
alkyl ester compound is a single compound or a mixture of two or more
compounds.
10 The plasticizer composition including a terephthalate-based material may be
provided. In particular, the terephthalate-based material may be used in an amount
selected from ranges of 1 wt% to 99 wt%, 20 wt% to 99 wt%, 40 wt% to 99 wt%, 50
wt% to 95 wt%, 60 wt% to 90 wt%, and the like, based on a total weight of the
plasticizer composition.
15 The terephthalate-based material may be a single compound selected from
the group consisting of di(2-ethylhexyl)terephthalate (DEHTP), diisononyl
terephthalate (DINTP), dibutyl terephthalate (DBTP), butyl isononyl terephthalate
(BINTP), butyl(2-ethylhexyl)terephthalate (BEHTP), and (2-ethylhexyl)isononyl
terephthalate (EHINTP) or a mixture of two or more of these compounds.
20 The terephthalate-based material may be a mixture of three terephthalatebased
materials, for example, a first mixture of di(2-ethylhexyl)terephthalate,
butyl(2-ethylhexyl)terephthalate, and dibutyl terephthalate, a second mixture of
diisononyl terephthalate, butyl isononyl terephthalate, and dibutyl terephthalate, or a
third mixture of di(2-ethylhexyl)terephthalate, (2-ethylhexyl)isononyl terephthalate,
25 and diisononyl terephthalate.
16
In particular, the first, second, and third mixtures may have a specific
composition ratio. The first mixture may include 3.0 mol% to 99.0 mol% of di(2-
ethylhexyl)terephthalate, 0.5 mol% to 96.5 mol% of butyl(2-
ethylhexyl)terephthalate, and 0.5 mol% to 96.5 mol% of dibutyl terephthalate, the
second mixture may include 3.0 mol% to 99.0 mol% of diisononyl 5 terephthalate, 0.5
mol% to 96.5 mol% of butyl isononyl terephthalate, and 0.5 mol% to 96.5 mol% of
dibutyl terephthalate, and the third mixture may include 3.0 mol% to 99.0 mol% of
di(2-ethylhexyl)terephthalate, 0.5 mol% to 96.5 mol% of (2-ethylhexyl)isononyl
terephthalate, and 0.5 mol% to 96.5 mol% of diisononyl terephthalate.
10 The composition ratio may be a mixed composition ratio produced by an
esterification reaction and may be an intended composition ratio in which a specific
compound is further mixed. The mixed composition ratio may be appropriately
adjusted according to desired physical properties.
The plasticizer composition includes a terephthalate-based material and an
15 epoxy-based alkyl ester compound. The epoxy-based alkyl ester compound may be
represented by Formula 1 below and have an iodine value (I.V.) of less than 4 g
I2/100 g.

20 wherein, in Formula 1, R1 is a C8-C20 alkyl group or an alkyl group
containing one or more epoxy groups, and R2 is a C4 or C8 alkyl group.
The epoxy-based alkyl ester compound may have an oxirane value (O.V.) of
6.0% or more, 6.3% or more, preferably, 6.5% or more. In addition, the oxirane
17
value may vary according to the number of epoxy groups included in a substituent
denoted as R1 in Formula 1, may be measured by titration, and may be measured by a
method of ASTM D1562-04 using a sample and an acid solution.
In addition, the iodine value of the epoxy-based alkyl ester compound may
be less than 4 g I2/100 g, preferably, 3.8 I2/100 g or less. The iodine value refers 5 rs to
the content of double bonds present in molecules, and may be obtained from values
measured by titration through iodination of the double bonds.
The measured iodine value and oxirane value may be important factors
when the epoxy-based alkyl ester compound is applied to the plasticizer composition.
10 In particular, when the iodine value of the epoxy-based alkyl ester compound is 4 g
I2/100 g or more, compatibility of the plasticizer composition with a resin may be
significantly reduced and thus the plasticizer composition may not be used as a
plasticizer. When the iodine value of the epoxy-based alkyl ester compound is less
than 4 g I2/100 g, mechanical and physical properties, such as tensile strength,
15 elongation rate, absorption rate, and the like, may be enhanced. In addition, the
oxirane value may also have a technical significance similar to that of the iodine
value and may have a similar effect.
The iodine value may refer to the content of double bonds, and the content
of double bonds may be the content of double bonds remaining after performing an
20 epoxidation reaction, such as epoxidation of vegetable oil, epoxidation of fatty acid
alkyl esters, or the like. That is, an oxirane value and an iodine value may be
indexes for a degree to which epoxidation proceeds, may be associated with each
other to some extent, and may be theoretically in inverse proportion to each other.
However, double bonds of vegetable oil or fatty acid alkyl esters may
25 substantially vary according to material, and thus the two parameters may not
18
accurately form an inverse proportion relation or a trade-off relation, and, of two
materials, a material with a higher iodine value may also have a higher oxirane value.
Thus, the epoxy-based alkyl ester compound having iodine and oxirane values within
the above-described ranges may be applied to the plasticizer composition.
Meanwhile, the epoxy-based alkyl ester compound may have 5 ve an epoxidation
index (E.I.) of 1.5 or more.
As described above, the iodine value and the oxirane value may satisfy the
above-described relation, and, simultaneously, the epoxidation index may satisfy a
range of 1.5 or more. The term "epoxidation index" as used herein refers to a ratio
10 of oxirane value to iodine value of the epoxy-based alkyl ester compound, and may
be a ratio of double bonds epoxidated by epoxidation to remaining unreacted double
bonds.
As described above, when the epoxidation index is less than 1.5 due to a
small amount of an oxirane or a high iodine value, or when epoxidation itself does
15 not proceed, hardness of the plasticizer composition increases and thus a plasticizing
effect thereof may be significantly deteriorated, and migration loss and volatile loss
properties may also be significantly deteriorated.
In particular, the epoxidation index, which is a ratio (O.V./I.V.) of an
oxirane value to an iodine value, may be 1.5 or more. That is, when a value
20 obtained by dividing the oxirane value of the epoxy-based alkyl ester compound by
the iodine value thereof is 1.5 or more, a more suitable plasticizer composition may
be obtained, and, in particular, the plasticizer composition may tend to have
increased compatibility with a resin.
The epoxy-based alkyl ester compound may be an epoxidized fatty acid
25 alkyl ester (eFAAE), and, in particular, may be represented by Formula 1 above,
19
"alkyl" of the epoxy-based alkyl ester compound may have 4 or 8 carbon atoms.
However, in the present invention, R2 of Formula 1 may have 4 to 8 carbon
atoms, and is preferably a butyl group or a 2-ethylhexyl group. In addition, the
epoxy-based alkyl ester compound of Formula 1 may be a mixed composition
including two or more compounds, and the mixed composition including 5 two or
more compounds may be a mixture of a compound having 4 carbon atoms and a
compound having 8 carbon atoms. When R2 of Formula 1 is a C4 or C8 group, the
plasticizer composition may have excellent absorption properties and thus exhibit
less of a gelling phenomenon, may exhibit enhanced processability, excellent basic
10 mechanical and physical properties such as tensile strength or elongation rate, and, in
particular, may exhibit excellent migration or volatile loss properties.
In this regard, a weight ratio of the terephthalate-based material and the
epoxy-based alkyl ester compound included in the plasticizer composition may range
from 99:1 to 1:99, 99:1 to 20:80, or 99:1 to 40:60, preferably, 95:5 to 50:50 or 90:10
15 to 60:40.
As described above, when the mixed plasticizer composition of a
terephthalate-based material and an epoxy-based alkyl ester compound is used, high
tensile strength and elongation rate may be obtained, improved effects in terms of
migration and volatile loss may be obtained, and an absorption rate may be
20 controlled and thus processability may also be enhanced.
Method of Preparing a Plasticizer Composition
According to an embodiment of the present invention, there is provided a
method of preparing a plasticizer composition, including: preparing a terephthalate25
based material; preparing an epoxy-based alkyl ester compound represented by
20
Formula 1 below by performing an esterification reaction on epoxidized oil and a C4
or C8 primary alkyl alcohol; and mixing the terephthalate-based material and the
epoxy-based alkyl ester compound in a weight ratio of 99:1 to 1:99, in which the
epoxy-based alkyl ester compound is a single compound or a mixture of two or more
5 compounds.
The preparing of the terephthalate-based material and the preparing of the
epoxy-based alkyl ester compound may be separately performed, and the materials
may be directly prepared through an esterification reaction and/or a transesterification
reaction.
10 The terephthalate-based material may be prepared through a direct
esterification reaction between terephthalic acid and one or more alcohols selected
from primary alkyl alcohols containing 4 to 12 carbon atoms, or a trans-esterification
reaction between a terephthalate and a primary alkyl alcohol containing 4 to 12
carbon atoms. In addition, the epoxy-based alkyl ester compound may be prepared
15 by a trans-esterification reaction between epoxidized oil and a primary alkyl alcohol
containing 4 or 8 carbon atoms.
As a terephthalate used as a raw material to prepare the terephthalate-based
material, an alkyl group of substituted ester groups at opposite sides of a benzene
ring may have 1 to 12 carbon atoms, preferably, 4 to 12 carbon atoms. The C4-C12
20 primary alkyl alcohol may be one or more selected from the group consisting of
butyl alcohol, isobutyl alcohol, 2-ethylhexyl alcohol, octyl alcohol, and isononyl
alcohol.
In addition, the primary alkyl alcohol containing 4 to 8 carbon atoms used
as a raw material to prepare the epoxy-based alkyl ester compound may be one or
25 more selected from the group consisting of butyl alcohol, isobutyl alcohol, 2-
21
ethylhexyl alcohol, and octyl alcohol. In this case, an alkyl group of the alcohol
may correspond to R2 of Formula 1 in the epoxy-based alkyl ester compound of
Formula 1 after the reaction is completed.
The epoxidized oil may be, for example, epoxidized soybean oil, epoxidized
castor oil, epoxidized linseed oil, epoxidized palm oil, epoxidized 5 ed stearic acid,
epoxidized oleic acid, epoxidized tall oil, epoxidized linoleic acid, or a mixture
thereof, and vegetable oil may be a compound into which a certain content of epoxy
groups is introduced through an epoxidation reaction.
The epoxidized oil may be, for example, represented by Formula 2 below,
10 and may contain three ester groups in a single molecule and include a certain content
of epoxy groups.

The epoxidized oil of Formula 2 is provided as one example.
15 In addition, the epoxidized oil may have an iodine value of less than 4 g
I2/100 g, and the iodine value is unlikely to vary during a trans-esterification reaction
and thus may be almost the same as the iodine value of the epoxy-based alkyl ester
compound, which is a reaction product. Characteristics of the iodine value are the
same as those of the iodine value of the epoxy-based alkyl ester compound as
20 described above.
When a trans-esterification reaction occurs between the epoxidized oil and
22
the C4 or C8 alkyl alcohol, all the three ester groups may be separated, and,
accordingly, three or more epoxy-based ester compounds in which the alkyl group of
the alcohol is newly linked may be formed.
The term "trans-esterification reaction" as used herein refers to a reaction in
which, as described in Reaction Scheme 1, an alcohol 5 ohol reacts with an ester group and
thus R" of the ester group is interchanged with R' of the alcohol:

According to an embodiment of the present invention, when the trans10
esterification reaction occurs, three types of ester compositions may be produced
according to three cases in which an alkoxide of an alcohol attacks carbon atoms of
two ester groups (RCOOR") present in an ester-based compound; an alkoxide of an
alcohol attacks carbon atoms of an ester group (RCOOR") present in an ester-based
compound; and there is no reaction therebetween.
15 In addition, the trans-esterification reaction is advantageous in that
wastewater problems are not caused and a reaction rate is high, compared to an
esterification reaction between an acid and an alcohol.
For example, the terephthalate-based material may be prepared by
producing a mixture of di(2-ethylhexyl)terephthalate, butyl(2-
20 ethylhexyl)terephthalate, and dibutyl terephthalate by the trans-esterification reaction
between di(2-ethylhexyl)terephthalate and butyl alcohol. The three terephthalates
may be included in the mixture in amounts of 3.0 wt% to 70 wt%, 0.5 wt% to 50
wt%, and 0.5 wt% to 85 wt%, respectively, in particular, 10 wt% to 50 wt%, 0.5 wt%
23
to 50 wt%, and 35 wt% to 80 wt%, respectively, based on a total weight of the
mixture. When the amounts of the three terephthalates are within the above ranges,
a terephthalate-based material (mixture) with high manufacturing efficiency, high
processability and a high absorption rate may be obtained.
In addition, a composition ratio of the mixture prepared by the tran5 sesterification
reaction may be controlled according to the amount of an alcohol
added.
The amount of the added alcohol may range from 0.1 parts by weight to
89.9 parts by weight, in particular, 3 parts by weight to 50 parts by weight, more
10 particularly, 5 parts by weight to 40 parts by weight, with respect to 100 parts by
weight of the terephthalate.
As the amount of the added alcohol increases, a mole fraction of the
terephthalate participating in the trans-esterification reaction increases, and thus the
amounts of the two terephthalates, which are reaction products, of the mixture may
15 increase, and the amount of unreacted terephthalate may decrease in accordance
therewith.
According to an embodiment of the present invention, a molar ratio of a
terephthalate to an alcohol, which are reactants, may range, for example, from
1:0.005 to 5.0, from 1:0.05 to 2.5, or from 1:0.1 to 1.0. When the molar ratio
20 thereof is within the above range, a plasticizer with high manufacturing efficiency
and significantly enhanced processability may be obtained.
However, the composition ratio of the mixture of three terephthalate-based
materials is not limited to the above-described ranges, and the composition ratio
thereof may be varied by further adding any one of the three terephthalates, and a
25 detailed description of suitable mixing composition ratios has already been provided
24
above.
According to an embodiment of the present invention, the transesterification
reaction may be performed at a reaction temperature of 120􀔨to 190􀔨,
preferably 135􀔨to 180􀔨, more preferably, 141􀔨to 179􀔨, for 10 minutes to 10
hours, preferably, 30 minutes to 8 hours, more preferably, for 1 hour to 5 6 hours.
When the reaction temperature and time are within the above ranges, a mixture of
terephthalate-based materials with a desired composition ratio may be effectively
obtained. At this time, the reaction time may be calculated from the time at which a
reaction starts at the reaction temperature after heating reactants.
10 The trans-esterification reaction may be performed in the presence of an
acid catalyst or a metal catalyst, and, in this case, the reaction time may be shortened.
The acid catalyst may be, for example, sulfuric acid, methanesulfonic acid,
p-toluenesulfonic acid, or the like, and the metal catalyst may be, for example, an
organic metal catalyst, a metal oxide catalyst, a metal salt catalyst, or a metal.
15 The metal component may be, for example, any one selected from the group
consisting of tin, titanium, and zirconium, or a mixture of two or more of these
metals.
In addition, the method may further include, after the trans-esterification
reaction, removing an unreacted alcohol and reaction byproducts, for example, an
20 ester-based compound represented by Formula 3, by distillation.
The distillation process may be, for example, two-stage distillation for
separating the alcohol and the reaction byproducts using a difference between boiling
points thereof.
As another example, the distillation process may be mixed distillation. In
25 this case, an ester-based plasticizer composition with a desired composition ratio
25
may be relatively stably obtained. The mixed distillation refers to simultaneous
distillation of butanol and reaction byproducts.
Generally, a trans-esterification reaction used to prepare an epoxy-based
alkyl ester compound is also applied in the same manner as in the reaction for
preparing a terephthalate-based material, but specific 5 reaction conditions and the like
may differ from each other. For example, there are differences as follows.
The trans-esterification reaction may be performed at a reaction temperature
of 40􀔨to 230􀔨, preferably 50􀔨to 200􀔨, more preferably, 70􀔨to 200􀔨, for 10
minutes to 10 hours, preferably, 30 minutes to 8 hours, more preferably, for 1 hour to
10 4 hours. When the reaction temperature and time are within the above ranges, a
desired epoxy-based alkyl ester compound may be effectively obtained. At this
time, the reaction time may be calculated from the time at which a reaction starts at
the reaction temperature after heating reactants.
In addition, the method may further include removing a polyhydric alcohol
15 and reaction byproducts produced after the trans-esterification reaction and the
unreacted alcohol by purification, washing, and distillation.
The purification process may be performed by, in particular, cooling to and
maintaining at a temperature of 80􀔨to 100􀔨for a certain period of time after the
trans-esterification reaction. In this case, layer separation occurs wherein an upper
20 layer may include an epoxy-based alkyl ester, and an alcohol, and a lower layer may
include glycerin and other byproducts. Next, to neutralize a catalyst, neutralization
and washing may be induced by adding an aqueous solution for neutralizing a
catalyst.
The neutralization and washing processes may be performed after, first,
25 separating the lower layer mainly including reaction byproducts, and in the
26
neutralization and washing processes, the byproducts included in the lower layer may
be dissolved in water to be discharged, and through a subsequently repeated washing
process, the unreacted alcohol and water may be recovered and removed.
However, it may be necessary to vary the neutralization and washing
processes according to the number of carbon atoms of an alcohol 5 used in the transesterification
reaction.
For example, in a case in which butanol with 4 carbon atoms is used, when
the neutralization and washing processes are immediately performed, wastewater
generation problems occur, and thus, butanol may be previously removed by
10 distillation. However, in this case, catalytic activity remains, and thus there may be
other problems, i.e., occurrence of an inverse reaction between glycerol as a reaction
byproduct and an epoxy-based alkyl ester as a reaction product to produce an
epoxidized oil-like material such as a diglyceride, a triglyceride, or the like, and,
accordingly, there is a need to pay attention to the design of manufacturing processes.
15 In addition, as another example, when 2-ethylhexyl alcohol with 8 carbon
atoms is used, the 2-ethylhexyl alcohol has low solubility in water, and thus there is
no wastewater generation problem and, accordingly, both the case of removing an
alcohol after the neutralization and washing processes and the case of performing the
neutralization and washing processes after removal of the lower layer including
20 reaction byproducts may be performed without severe problems.
In addition, in the case of preparing the epoxy-based alkyl ester compound,
physical properties of the prepared epoxy-based alkyl ester compound may vary
according to the type or amount of catalyst used, and physical properties, yield, or
quality of products may vary according to reaction time or the amount of a primary
25 alkyl alcohol reacted with epoxidized oil.
27
In particular, in the process of preparing an epoxy-based alkyl ester
compound, NaOMe may be preferably used as a catalyst, and, when sodium
hydroxide or potassium hydroxide is used as a catalyst, the color of the prepared
epoxy-based alkyl ester compound may not meet its standard, and an epoxidation
index, the amount of oxirane, and the like of the epoxy-based alkyl 5 l ester compound
may not have desired values.
In addition, the amount of the catalyst may range from 0.1 wt% to 2.0 wt%,
preferably, from 0.1 wt% to 1.0 wt%, with respect to a total weight of the epoxidized
oil which is a reaction raw material. When the amount of the catalyst is within the
10 above range, it may be most effective in terms of reaction rate, and, when the amount
of the catalyst is outside the above range, an epoxidation index and the like of the
epoxy-based alkyl ester compound may not meet quality standards due to a failure in
adjusting the amount of the catalyst.
In preparation of the epoxy-based alkyl ester compound, amounts of
15 epoxidized oil and a primary alkyl alcohol added may be an important factor. The
primary alkyl alcohol may be added in an amount of 30 parts by weight to 100 parts
by weight with respect to the amount of the epoxidized oil. When the amount of the
primary alkyl alcohol is less than 30 parts by weight, a reaction does not occur
efficiently, and thus residual epoxidized oil or impurities such as a dimerized
20 material of epoxidized oil, and the like may remain in an excess amount, and, when
the amount of the primary alkyl alcohol is 100 parts by weight or more, the amount
of a residual alcohol to be separated is greater than the amount of a product in the
purification process, and thus problems in terms of energy and manufacturing
efficiency may occur during the process.
25 As described above, after preparing the terephthalate-based material and the
28
epoxy-based alkyl ester compound, a process of mixing the two compounds may be
performed. A mixing ratio may be appropriately selected from ranges from 99:1 to
1:99, and the two compounds may be mixed in the above-described mixing weight
ratio.
In addition, the plasticizer compound according 5 to the present invention
may further include epoxidized oil, in addition to the terephthalate-based material
and the epoxy-based alkyl ester compound.
In the case of a mixed plasticizer composition of the terephthalate-based
material and the epoxy-based alkyl ester compound, thermal resistance from among a
10 variety of physical properties may be relatively poor, and such a thermal resistance
property may be compensated for by further adding the epoxidized oil.
The epoxidized oil may be, for example, epoxidized soybean oil, epoxidized
castor oil, epoxidized linseed oil, epoxidized palm oil, epoxidized stearic acid,
epoxidized oleic acid, epoxidized tall oil, epoxidized linoleic acid, or a mixture
15 thereof. Preferably, the epoxidized oil is epoxidized soybean oil (ESO) or
epoxidized linseed oil (ELO), but the present invention is not limited thereto.
In addition, the epoxidized oil may be included in an amount of 1 part by
weight to 100 parts by weight, preferably, 10 parts by weight to 100 parts by weight,
preferably, 20 parts by weight to 100 parts by weight, with respect to 100 parts by
20 weight of the mixture of the terephthalate-based material and the epoxy-based alkyl
ester compound. When the amount of the epoxidized oil is within the above ranges,
a plasticizer compound with suitably excellent mechanical and physical properties
and thermal resistance properties may be obtained.
Furthermore, when a terephthalate-based product and epoxidized oil are
25 used in combination, an overall freezing point of the plasticizer composition may be
29
further reduced, and thus the plasticizer composition has a much lower freezing point
than that of an epoxy-based plasticizer composition, and thus a plasticizer
composition without limitation on use even during the winter season may be
provided.
5
Resin Composition
According to an embodiment of the present invention, there is provided a
resin composition including: 100 parts by weight of a resin; and 5 parts by weight to
150 parts by weight of the above-described plasticizer composition.
The resin may be one or more resin selected from ethylene vinyl 10 l acetate,
polyethylene, polypropylene, polyketone, polyvinyl chloride, polystyrene,
polyurethane, and thermoplastic elastomers, and the plasticizer composition may be
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, with
15 respect to 100 parts by weight of the resin, thereby providing a resin composition
effective in compound formulation, sheet formulation, and plastisol formulation.
Since the resin composition includes the above-described plasticizer
compound, the resin composition may be applied to a variety of applications, such as
flooring materials, wallpaper, interior materials for automobiles, sheets, films, hoses,
20 electric wires, and the like, and may exhibit basic mechanical and physical properties
such as tensile strength, elongation rate, plasticizing efficiency, and volatile loss that
are the same as or superior to those of existing plasticizers.
According to an embodiment of the present invention, the resin composition
may further include a filler.
25 The amount of the filler may range from 0 parts by weight to 300 parts by
30
weight, preferably, 50 parts by weight to 200 parts by weight, more preferably, 100
parts by weight to 200 parts by weight, based on 100 parts by weight of the resin.
The filler may be any filler known in the art and is not particularly limited.
For example, the filler may be one selected from silica, magnesium carbonate,
calcium carbonate, hard charcoal, talc, magnesium hydroxide, titanium dioxide5 ,
magnesium oxide, calcium hydroxide, aluminum hydroxide, aluminum silicate,
magnesium silicate, barium sulfate, and mixtures thereof.
The resin composition may further include other additives such as a
stabilizer and the like according to need.
10 The amount of the other additives such as a stabilizer and the like may range,
for example, from 0 parts by weight to 20 parts by weight, preferably, from 1 part by
weight to 15 parts by weight, based on 100 parts by weight of the resin.
The stabilizer may be, for example, a calcium-zinc-based (Ca-Zn-based)
stabilizer such as a Ca-Zn composite stearate, or the like, but is not particularly
15 limited thereto.

I/We Claim:
􀫺Claim 1􀫻
A plasticizer composition comprising: a terephthalate-based material; and
an epoxy-based alkyl ester compound represented by Formula 1 below
wherein a weight ratio of the terephthalate-based material to the epoxy5 -
based alkyl ester compound is 99:1 to 1:99, and the epoxy-based alkyl ester
compound is a single compound or a mixture of two or more compounds:

10 wherein, in Formula 1, R1 is a C8-C20 alkyl group or an alkyl group
containing one or more epoxy groups, and R2 is a C4 or C8 alkyl group.
􀫺Claim 2􀫻
The plasticizer composition of claim 1, wherein the weight ratio of the
15 terephthalate-based material to the epoxy-based alkyl ester compound is 95:5 to
20:80.
􀫺Claim 3􀫻
The plasticizer composition of claim 1, wherein the terephthalate-based
20 material is a single compound selected from the group consisting of di(2-
ethylhexyl)terephthalate (DEHTP), diisononyl terephthalate (DINTP), dibutyl
terephthalate (DBTP), butyl isononyl terephthalate (BINTP), butyl(2-
32
ethylhexyl)terephthalate (BEHTP), and (2-ethylhexyl)isononyl terephthalate
(EHINTP) or a mixture of two or more of these compounds.
􀫺Claim 4􀫻
The plasticizer composition of claim 3, wherein the terephthalate-5 -based
material is a first mixture of di(2-ethylhexyl)terephthalate, butyl(2-
ethylhexyl)terephthalate, and dibutyl terephthalate, a second mixture of diisononyl
terephthalate, butyl isononyl terephthalate, and dibutyl terephthalate, or a third
mixture of di(2-ethylhexyl)terephthalate, (2-ethylhexyl)isononyl terephthalate, and
10 diisononyl terephthalate.
􀫺Claim 5􀫻
The plasticizer composition of claim 1, wherein the epoxy-based alkyl ester
compound has an iodine value of less than 4 g I2/100 g.
15
􀫺Claim 6􀫻
The plasticizer composition of claim 1, wherein the epoxy-based alkyl ester
compound has an epoxidation index (E.I.) of 1. 5 or more.
20 􀫺Claim 7􀫻
The plasticizer composition of claim 1, further comprising epoxidized oil.
􀫺Claim 8􀫻
The plasticizer composition of claim 7, wherein the epoxidized oil may be
33
included in an amount of 1 part by weight to 100 parts by weight with respect to a
weight of a mixture of the terephthalate-based material and the epoxy-based alkyl
ester compound.
􀫺5 Claim 9􀫻
The plasticizer composition of claim 7, wherein the epoxidized oil
comprises one or more selected from the group consisting of epoxidized soybean oil,
epoxidized castor oil, epoxidized linseed oil, epoxidized palm oil, epoxidized stearic
acid, epoxidized oleic acid, epoxidized tall oil, and epoxidized linoleic acid.
10
􀫺Claim 10􀫻
A method of preparing a plasticizer composition, the method comprising:
preparing a terephthalate-based material;
preparing an epoxy-based alkyl ester compound represented by Formula 1
15 below by performing an esterification reaction on epoxidized oil and a C4 or C8
primary alkyl alcohol; and
mixing the terephthalate-based material and the epoxy-based alkyl ester
compound in a weight ratio of 99:1 to 1:99,
wherein the epoxy-based alkyl ester compound is a single compound or a
20 mixture of two or more compounds,

34
wherein, in Formula 1, R1 is a C8-C20 alkyl group or an alkyl group
containing one or more epoxy groups, and R2 is a C4 or C8 alkyl group.
􀫺Claim 11􀫻
The method of claim 10, wherein the C4 or C8 primary alkyl alcoho5 l
comprises one or more selected from the group consisting of butyl alcohol, isobutyl
alcohol, 2-ethylhexyl alcohol, and octyl alcohol.
􀫺Claim 12􀫻
10 The method of claim 10, wherein the terephthalate-based material is
prepared through a direct esterification reaction between terephthalic acid and one or
more alcohols selected from primary alkyl alcohols containing 4 to 12 carbon atoms;
or through a trans-esterification reaction between a terephthalate and a primary alkyl
alcohol containing 4 to 12 carbon atoms.
15
􀫺Claim 13􀫻
The method of claim 10, wherein the primary alkyl alcohol containing 4 to
12 carbon atoms comprises one or more selected from the group consisting of butyl
alcohol, isobutyl alcohol, 2-ethylhexyl alcohol, octyl alcohol, and isononyl alcohol.
20
􀫺Claim 14􀫻
The method of claim 10, wherein the epoxidized oil comprises one or more
selected from the group consisting of epoxidized soybean oil, epoxidized castor oil,
epoxidized linseed oil, epoxidized palm oil, epoxidized stearic acid, epoxidized oleic
35
acid, epoxidized tall oil, and epoxidized linoleic acid.
􀫺Claim 15􀫻
A resin composition comprising: 100 parts by weight of a resin; and 5 parts
by weight to 150 parts by weight of the plasticizer 5 r composition of claim 1.
􀫺Claim 16􀫻
The resin composition of claim 15, wherein the resin comprises one or more
selected from the group consisting of ethylene vinyl acetate, polyethylene,
10 polypropylene, polyketone, polyvinyl chloride, polystyrene, polyurethane, and
thermoplastic elastomers.