DESCRIPTION
PLASTICIZER COMPOSITION AND RESIN COMPOSITION, AND
PREPARATION METHOD THEREOF
5
TECHNICAL FIELD
Cross-reference to Related Applications
[0001] This application claims the benefit of Korean Patent
Application Nos. 10-2015-0021783, filed on February 12, 2015,
10 10-2015-0041794, filed on March 25, 2015, 10-2015-0113875,
filed on August 12, 2015, and 10-2015-0144889, filed on
October 16, 2015, in the Korean Intellectual Property Office,
the disclosure of which is incorporated herein in its
entirety by reference.
15 Technical Field
[0002] The present invention relates to a plasticizer
composition and a resin composition, and a preparation method
thereof.
BACKGROUND ART
20 [0003] 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,
25 research into plasticizer compositions, which may replace
3
phthalate-based plasticizers such as terephthalate-based
plasticizers, adipate-based plasticizers, and other polymerbased
plasticizers, has continued.
[0004] In order to manufacture flooring materials, wallpaper,
sheet products, an appropriate plasticizer must be used i5 n
consideration of discoloration, migration, and processability.
A plasticizer, a filler, a stabilizer, a viscosity reducing
agent, a dispersant, an antifoaming agent, and a foaming
agent are mixed with a PVC resin according to properties
10 required by industry in various use areas, for example,
tensile strength, elongation rate, light resistance,
migration, gelling property, or processability.
[0005] For example, in a case in which inexpensive dioctyl
terephthalate is used among plasticizer compositions that are
15 applicable to PVC, its viscosity is high, the absorption rate
of the plasticizer is relatively low, and migration is also
not good.
[0006] Thus, there is a continuous need to research into
techniques by which a product better than the dioctyl
20 terephthalate or a novel composition product including
dioctyl terephthalate is developed and optimally used as a
plasticizer for a vinyl chloride-based resin.
DISCLOSURE OF THE INVENTION
TECHNICAL PROBLEM
25 [0007] As a result of continuous research into plasticizers,
4
the present inventors found a plasticizer composition which
may improve poor physical properties that have been ascribed
to structural limitations, thereby leading to the completion
of the present invention.
[0008] The present invention provides a 5 plasticizer which
may improve physical properties, such as plasticizing
efficiency, migration, and gelling property, required for a
sheet formulation when used as a plasticizer of a resin
composition, a preparation method thereof, and a resin
10 composition including the plasticizer.
TECHNICAL SOLUTION
[0009] According to an aspect of the present invention,
there is provided a plasticizer composition including a
terephthalate-based material; and a Citrate-based material,
15 wherein a weight ratio of the terephthalate-based material to
the Citrate-based material is in a range of 99:1 to 1:99.
[0010] The weight ratio of the terephthalate-based material
to the Citrate-based material may be in a range of 95:5 to
50:50.
20 [0011] The weight ratio of the terephthalate-based material
to the Citrate-based material may be in a range of 95:5 to
60:40.
[0012] The terephthalate-based material may include a single
compound selected from the group consisting of di(2-
25 ethylhexyl)terephthalate (DEHTP or DOTP), diisononyl
5
terephthalate (DINTP), dibutyl terephthalate (DBTP), butyl
isononyl terephthalate (BINTP), butyl(2-
ethylhexyl)terephthalate (BEHTP or BOTP), and (2-
ethylhexyl)isononyl terephthalate (EHINTP or OINTP), or a
5 mixture in which one or more compounds are mixed.
[0013] The single compound may be di(2-
ethylhexyl)terephthalate or diisononyl terephthalate.
[0014] The mixture may be a first mixture in which di(2-
ethylhexyl)terephthalate, butyl(2-ethylhexyl)terephthalate,
10 and dibutyl terephthalate are mixed, a second mixture in
which diisononyl terephthalate, butyl isononyl terephthalate,
and dibutyl terephthalate are mixed, or a third mixture in
which di(2-ethylhexyl)terephthalate, (2-ethylhexyl)isononyl
terephthalate, and diisononyl terephthalate are mixed.
15 [0015] 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.
[0016] The second mixture may include 3.0 mol% to 99.0 mol%
20 of diisononyl terephthalate; 0.5 mol% to 96.5 mol% of butyl
isononyl terephthalate; and 0.5 mol% to 96.5 mol% of dibutyl
terephthalate.
[0017] 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
25 (2-ethylhexyl)isononyl terephthalate; and 0.5 mol% to 96.5
6
mol% of diisononyl terephthalate.
[0018] The Citrate-based material may include any one
selected from the group consisting of a hybrid alkylsubstituted
Citrate-based material having 4 to 9 carbon atoms
and a non-hybrid alkyl-substituted Citrate-5 based material
having 4 to 9 carbon atoms.
[0019] The Citrate-based material may be a non-hybrid alkylsubstituted
Citrate-based material having 4 to 9 carbon atoms,
and an alkyl group having 4 to 9 carbon atoms of the Citrate10
based material may be a linear chain or a branched chain.
[0020] The plasticizer composition may further include an
epoxidized oil.
[0021] The epoxidized oil may be included in an amount of 1
parts by weight to 100 parts by weight based on 100 parts by
15 weight of the plasticizer composition.
[0022] The epoxidized oil may include at least one selected
from the group consisting of epoxidized soybean oil,
epoxidized castor oil, epoxidized linseed oil, epoxidized
palm oil, epoxidized stearic acid, epoxidized oleic acid,
20 epoxidized tall oil, and epoxidized linoleic acid.
[0023] According to another aspect of the present invention,
there is provided a method of preparing a plasticizer
composition including preparing a terephthalate-based
material and a Citrate-based material; and obtaining a
25 plasticizer compound by blending the terephthalate-based
7
material and the Citrate-based material in a weight ratio of
99:1 to 1:99, wherein the terephthalate-based material is a
single compound or a mixture.
[0024] When the terephthalate-based material is the mixture,
the terephthalate compound may be prepared by a 5 direct
esterification reaction in which terephthalic acid reacts
with at least one alcohol selected from the group consisting
of 2-ethylhexyl alcohol, isononyl alcohol, butyl alcohol, and
isobutyl alcohol; or a transesterification reaction in which
10 any one terephthalate selected from di(2-
ethylhexyl)terephthalate or diisononyl terephthalate reacts
with any one alcohol selected from butyl alcohol or isobutyl
alcohol.
[0025] According to another aspect of the present invention,
15 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 plasticizer composition.
[0026] The resin may include at least one selected from the
group consisting of ethylene vinyl acetate, polyethylene,
20 polypropylene, polyvinyl chloride, polystyrene, polyurethane,
and a thermoplastic elastomer.
[0027] The resin composition may be a material of at least
one product selected from the group consisting of electric
wires, flooring materials, automotive interior materials,
25 films, sheets, wallpaper, and tubes.
8
ADVANTAGEOUS EFFECTS
[0028] A plasticizer composition according to an embodiment
of the present invention may provide excellent physical
properties, such as migration resistance and volatility
resistance, as well as excellent plasticizing 5 efficiency,
tensile strength, and elongation rate when used in a resin
composition.
BRIEF DESCRIPTION OF THE DRAWINGS
[0029] The following drawings attached to the specification
10 illustrate preferred examples of the present invention by
example, and serve to enable technical concepts of the
present invention to be further understood together with
detailed description of the invention given below, and
therefore the present invention should not be interpreted
15 only with matters in such drawings.
[0030] FIG. 1 is an image illustrating the results of heat
resistance tests for resins including plasticizer
compositions according to the present invention;
[0031] FIG. 2 is an image illustrating the results of heat
20 resistance tests for the resins including the plasticizer
compositions according to the present invention; and
[0032] FIG. 3 is an image illustrating the results of
thermal stability tests for the resins including the
plasticizer compositions according to the present invention.
25 MODE FOR CARRYING OUT THE INVENTION
9
[0033] Hereinafter, the present invention will be described
in detail.
[0034] First, the present invention has technical features
that provide a plasticizer composition which may improve poor
physical properties that have been ascribed to 5 structural
limitations.
[0035] According to an embodiment of the present invention,
a plasticizer composition including a terephthalate-based
material may be provided. Specifically, the terephthalate10
based material may be used in an amount selected from a range
of 1 wt% to 99 wt%, 20 wt% to 99 wt%, 40 wt% to 99 wt%, 50
wt% to 95 wt%, or 60 wt% to 90 wt% based on a total weight of
the composition.
[0036] The terephthalate-based material, for example, may
15 have a terminal group independently selected from an alkyl
group having 1 to 12 carbon atoms, an alkyl group having 3 to
11 carbon atoms, an alkyl group having 4 to 10 carbon atoms,
an alkyl group having 8 to 10 carbon atoms, an alkyl group
having 8 to 9 carbon atoms, or an alkyl group having 8 carbon
20 atoms.
[0037] The terephthalate-based material may be a single
compound selected from the group consisting of di(2-
ethylhexyl)terephthalate (DEHTP or DOTP), diisononyl
terephthalate (DINTP), dibutyl terephthalate (DBTP), butyl
25 isononyl terephthalate (BINTP), butyl(2-
10
ethylhexyl)terephthalate (BEHTP or BOTP), and (2-
ethylhexyl)isononyl terephthalate (EHINTP or OINTP), or a
mixture in which one or more compounds are mixed.
[0038] Specifically, in a case in which the terephthalatebased
material is the single compound, the 5 terephthalatebased
material may be di(2-ethylhexyl)terephthalate or
diisononyl terephthalate. In a case in which the
terephthalate-based material is the mixture, the mixture may
be one in which three kinds of the terephthalate-based
10 materials are mixed, and, for example, the mixture may be a
first mixture in which di(2-ethylhexyl)terephthalate,
butyl(2-ethylhexyl)terephthalate, and dibutyl terephthalate
are mixed, a second mixture in which diisononyl terephthalate,
butyl isononyl terephthalate, and dibutyl terephthalate are
15 mixed, or a third mixture in which di(2-
ethylhexyl)terephthalate, (2-ethylhexyl)isononyl
terephthalate, and diisononyl terephthalate are mixed.
[0039] Specifically, the first to third mixture may have a
specific composition ratio, wherein the first mixture may
20 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 terephthalate; 0.5 mol% to
25 96.5 mol% of butyl isononyl terephthalate; and 0.5 mol% to
11
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%
5 of diisononyl terephthalate.
[0040] The composition ratio may be a mixed composition
ratio generated 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
10 appropriately adjusted to match the desired physical
properties.
[0041] Also, according to an embodiment of the present
invention, the plasticizer composition may further include a
Citrate-based material, and the Citrate-based material may
15 include at least one compound selected from the group
consisting of a hybrid alkyl-substituted Citrate-based
material having 4 to 9 carbon atoms and a non-hybrid alkylsubstituted
Citrate-based material having 4 to 9 carbon atoms.
[0042] Examples of the hybrid alkyl-substituted Citrate20
based material having 4 to 9 carbon atoms may be citrate
having a substituent in which alkyl groups having 4 and 8
carbon atoms are combined, such as 1,2-dibutyl 3-(2-
ethylhexyl)2-hydroxypropane-1,2,3-tricarboxylate, 1,3-dibutyl
2-(2-ethylhexyl)2-hydroxypropane-1,2,3-tricarboxylate, 1-
25 butyl 2,3-bis(2-ethylhexyl)2-hydroxypropane-1,2,3-
12
tricarboxylate, or 2-butyl 1,3-bis(2-ethylhexyl)2-
hydroxypropane-1,2,3-tricarboxylate; and citrate having a
substituent in which alkyl groups having 5 and 7 carbon atoms
are combined, such as 1,2-dipentyl 3-heptyl 2-hydroxypropane-
1,2,3-tricarboxylate, 1,3-dipentyl 2-heptyl 2-5 hydroxypropane-
1,2,3-tricarboxylate, 1-pentyl 2,3-diheptyl 2-hydroxypropane-
1,2,3-tricarboxylate, or 2-butyl 1,3-diheptyl 2-
hydroxypropane-1,2,3-tricarboxylate. In addition, citrate
having a substituent, in which two alkyl groups having a
10 different carbon number selected from 4 to 9 are combined,
may be used, and the alkyl group may be a linear chain or a
branched chain.
[0043] With respect to the non-hybrid alkyl-substituted
Citrate-based material having 4 to 9 carbon atoms, the alkyl
15 group having 4 to 9 carbon atoms may be a linear chain or a
branched chain, and, for example, tributyl citrate (TBC),
tripentyl citrate (TPC), trihexyl citrate (THC), triheptyl
citrate (THC), trioctyl citrate (TOC), and trinonyl citrate
(TNC) may be used. The butyl group to nonyl group may
20 include their respective structural isomers, for example, an
isobutyl group with respect to the butyl group and a 2-
ethylhexyl group with respect to the octyl group.
[0044] It may be desirable to use the non-hybrid alkylsubstituted
Citrate-based material having 4 to 9 carbon atoms
25 in comparison to the hybrid alkyl-substituted Citrate-based
13
material, although the present invention is not limited
thereto. Also, tributyl citrate and/or tri(2-
ethylhexyl)citrate may be more frequently used.
[0045] Trialkyl citrate or di-n-alkyl-m-alkyl citrate may be
used with the hybrid or non-hybrid alkyl-5 substituted Citratebased
material, wherein, in a case in which an acetyl group
is present in the Citrate-based material, processability and
gelling property may be deteriorated due to the reduction of
physical properties, particularly, plasticizing efficiency,
10 of the plasticizer.
[0046] In other words, in a case in which the Citrate-based
material is an acetyl citrate compound substituted with an
acetyl group instead of hydrogen of the remaining hydroxyl
group in addition to three ester groups, reduction in various
15 aspects, such as marketability, economic efficiency, and
physical properties, may be an issue due to limitations such
as the reduction of the plasticizing efficiency, an increased
input of the plasticizer to overcome the reduction of the
plasticizing efficiency, and the resulting price increase.
20 [0047] Herein, the terephthalate-based material and the
Citrate-based material in the plasticizer composition may be
included in a weight ratio of 99:1 to 1:99, may be included
in a weight ratio of 99:1 to 20:80, 99:1 to 40:60, 99:1 to
50:50, or 99:1 to 60:40, and, for example, may be included in
25 a ratio of 95:5 to 50:50 or 90:10 to 60:40.
14
[0048] The plasticizer composition includes the
terephthalate-based material and the Citrate-based material,
and may further include epoxidized oil. The epoxidized oil
may be included in an amount of 1 parts by weight to 100
parts by weight, preferably, 1 parts by weight to 80 5 0 parts by
weight, based on 100 parts by weight of the plasticizer
composition.
[0049] With respect to the mixed plasticizer composition of
the terephthalate-based material and the Citrate-based
10 material, heat resistance properties among various physical
properties may be relatively poor, and the poor heat
resistance properties may be compensated by further including
the epoxidized oil. In a case in which the amount of the
epoxidized oil is greater than 100 parts by weight, physical
15 properties, such as migration resistance, volatility
resistance, or tensile strength, of the mixed plasticizer
composition may be relatively deteriorated, and, in a case in
which the amount of the epoxidized oil included is less than
1 parts by weight, the poor heat resistance properties may
20 not be compensated. However, if the epoxidized oil is
included in the range of 1 parts by weight to 80 parts by
weight, properties such as heat resistance, tensile strength,
or volatility resistance may be optimized. But, the
plasticizer composition can have excellent properties unless
25 the epoxidized oil is greater than 100 parts by weight.
15
[0050] Examples of the epoxidized oil may be 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 thereof. For example, the epoxidized soybean 5 oil
(ESO) or the epoxidized linseed oil (ELO) may be used, but
the present invention is not limited thereto.
[0051] A blending method may be used as a method of
preparing the plasticizer composition in the present
10 invention, wherein the blending method, for example, is as
follows:
[0052] A terephthalate-based material and a Citrate-based
material are prepared, and the plasticizer composition may be
prepared by blending the terephthalate-based material and the
15 Citrate-based material in a weight ratio of 1:99 to 99:1,
wherein the terephthalate-based material is characterized in
that it is a single compound or a mixture.
[0053] In a case in which the terephthalate-based material
is the single compound, the terephthalate compound may be
20 prepared by a direct esterification reaction in which
terephthalic acid reacts with at least one alcohol selected
from the group consisting of 2-ethylhexyl alcohol, isononyl
alcohol, butyl alcohol, and isobutyl alcohol.
[0054] The direct esterification reaction may include:
25 adding terephthalic acid to alcohol and then adding a
16
catalyst to react in a nitrogen atmosphere; removing
unreacted alcohol and neutralizing unreacted acid; and
dehydrating and filtering by vacuum distillation.
[0055] Also, the alcohol used in the blending method may be
used in an amount of 150 mol% to 500 mol%, 200 mol% 5 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 terephthalic acid.
[0056] Examples of the catalyst used in the blending method
may include at least one selected from the group consisting
10 of acid catalysts such as sulfuric acid, hydrochloric acid,
phosphoric acid, nitric acid, para-toluenesulfonic acid,
methanesulfonic acid, ethanesulfonic acid, propanesulfonic
acid, butanesulfonic acid, and alkyl sulfuric acid; metal
salts such as aluminum lactate, lithium fluoride, potassium
15 chloride, cesium chloride, calcium chloride, ferric chloride,
and aluminum phosphate; metal oxide such as heteropolyacid;
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
20 used as the catalyst.
[0057] An amount of the catalyst used may vary depending on
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
25 wt% to 4 wt% based on total 100 wt% of a reactant. With
17
respect to a non-uniform catalyst, the amount of the catalyst
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.
[0058] In this case, the reaction temperature may be in 5 a
range of 180ºC to 280ºC, 200ºC to 250ºC, or 210ºC to 230ºC.
[0059] In a case in which the terephthalate-based material
is the mixture, the terephthalate compound may be prepared by
the above-described direct esterification reaction and may
10 then be mixed; or the terephthalate compound may be prepared
by a transesterification reaction in which any one
terephthalate compound selected from di(2-
ethylhexyl)terephthalate or diisononyl terephthalate reacts
with any one alcohol selected from butyl alcohol or isobutyl
15 alcohol.
[0060] The expression “transesterification reaction” used in
the present invention denotes a reaction between alcohol and
ester to interchange R” of the ester with R’ in the alcohol,
as illustrated in the following Reaction Equation 1:
20 [0061] [Reaction Equation 1]
[0062] According to an embodiment of the present invention,
when the transesterification reaction is performed, three
18
kinds of ester compositions may be generated in three cases,
for example, the case in which alkoxide of the alcohol
attacks carbon atoms in two ester groups (RCOOR”) present in
the ester-based compound; the case in which alkoxide of the
alcohol attacks carbon atoms in one ester group (5 RCOOR”)
present in the ester-based compound; and the unreacted case
in which the reaction is not performed.
[0063] Also, since the transesterification reaction may not
cause wastewater problems in comparison to an esterification
10 reaction between acid and alcohol and may be performed under
no catalyst conditions, limitations when using an acid
catalyst may be resolved.
[0064] For example, a mixture of di(2-
ethylhexyl)terephthalate, butyl(2-ethylhexyl)terephthalate,
15 and dibutyl terephthalate may be generated by the
transesterification reaction of di(2-ethylhexyl)terephthalate
and butyl alcohol, and the three kinds of terephthalates may
be formed in an amount of 3.0 wt% to 70 wt%, 0.5 wt% to 50
wt%, and 0.5 wt% to 85 wt%, for example, 10 wt% to 50 wt%,
20 0.5 wt% to 50 wt%, and 35 wt% to 80 wt%, based on a total
weight of the mixture, respectively. A terephthalate-based
material (mixture) having high process efficiency, excellent
processability, and excellent absorption time may be obtained
within the above ranges.
25 [0065] Furthermore, with respect to the mixture prepared by
19
the transesterification reaction, the composition ratio of
the mixture may be controlled according to an amount of the
alcohol added.
[0066] The amount of the alcohol added may be in a range of
0.1 part by weight to 89.9 parts by weight, particularly, 5 3
parts by weight to 50 parts by weight, and, more particularly,
5 parts by weight to 40 parts by weight, based on 100 parts
by weight of the terephthalate compound.
[0067] With respect to the terephthalate compound, since the
10 mole fraction of the terephthalate compound participating in
the transesterification reaction may be increased as the
amount of the added alcohol increases, the amounts of the two
terephthalate compounds, as products in the mixture, may be
increased and, correspondingly, the amount of the unreacted
15 terephthalate compound may tend to be decreased.
[0068] According to an embodiment of the present invention,
a molar ratio of the terephthalate compound, as the reactant,
to the alcohol, for example, is in a range of 1:0.005 to
1:5.0, 1:0.05 to 1:2.5, or 1:0.1 to 1:1.0, and an ester
20 plasticizer composition having high process efficiency and an
excellent improving effect of processability may be obtained
within the above-described range.
[0069] However, the composition ratio of the mixture of the
three kinds of the terephthalate-based materials is not
25 limited to the above-described range, the composition ratio
20
may be changed by further adding any one of the three kinds
of terephthalates, and the possible mixed composition ratio
is the same as described above.
[0070] According to an embodiment of the present invention,
the transesterification reaction may be conducted in 5 a
temperature range of 120°C to 190°C, 135°C to 180°C, and, for
example, 141°C to 179°C for 10 minutes to 10 hours, 30
minutes to 8 hours, and, for example, 1 hour to 6 hours. The
mixture, as the terephthalate-based material having a desired
10 composition ratio, may be effectively obtained within the
above temperature and time ranges. In this case, the
reaction time may be calculated from the reaching point of
the reaction temperature after increasing the temperature of
the reactants.
15 [0071] The transesterification reaction may be conducted
under an acid catalyst or a metal catalyst, and, in this case,
the reaction time may be decreased.
[0072] The acid catalyst, for example, may be sulfuric acid,
methanesulfonic acid, or p-toluenesulfonic acid, and the
20 metal catalyst, for example, may be an organic metal catalyst,
a metal oxide catalyst, a metal salt catalyst, or a metal
itself.
[0073] The metal, for example, may be any one selected from
the group consisting of tin, titanium, and zirconium, or a
25 mixture of two or more thereof.
21
[0074] Also, the method may further include removing
unreacted alcohol after the transesterification reaction and
a reaction by-product, for example, an ester-based compound,
by distillation.
[0075] For example, the distillation may be a two-5 stage
distillation for separating the alcohol and the reaction byproduct
by using a difference of boiling points.
[0076] As another example, the distillation may be mixed
distillation. In this case, the ester plasticizer
10 composition having a desired composition ratio may be
relatively stably secured. The mixed distillation denotes
that butanol and the reaction by-product are distilled at the
same time.
[0077] The direct esterification reaction and the
15 transesterification reaction may also be used in the
preparation of the above-described hybrid or non-hybrid
citrate compound. In this case, similar to the
terephthalate-based material, the Citrate-based material may
also be prepared as a mixed composition having a
20 predetermined ratio, and the composition ratio of the mixture
generated may be controlled according to the adjustment of
the amount of alcohol as a reaction raw material. In
addition, in a case in which the Citrate-based material is
prepared by the direct esterification reaction or
25 transesterification reaction, the same contents as those used
22
in the preparation of the above-described terephthalate-based
material may be used.
[0078] The plasticizer composition thus prepared may provide
a resin composition that is effective to compound formulation,
sheet formulation, and plastisol formulation by 5 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 from the group consisting of
10 ethylene vinyl acetate, polyethylene, polypropylene,
polyvinyl chloride, polystyrene, polyurethane, and a
thermoplastic elastomer.
[0079] For example, the plasticizer composition may be used
in the manufacture of electric wires, flooring materials,
15 automotive interior materials, films, sheets, wallpaper, or
tubes.
[0080] Examples
[0081] Hereinafter, the present invention will be described
20 in detail according to specific examples. The invention may,
however, be embodied in many different forms and should not
be construed as being limited to the embodiments set forth
herein. Rather, these embodiments are provided so that this
disclosure will be thorough and complete, and will fully
25 convey the scope of the present invention to those skilled in
23
the art.
[0082] Preparation Example 1: Preparation of DOTP
[0083] 498.0 g of purified terephthalic acid (TPA), 1,170 g
of 2-ethylhexyl alcohol (2-EH) (molar ratio of TPA:5 2-
EH=1.0:3.0), and 1.54 g (0.31 part by weight based on 100
parts by weight of the TPA) of a titanium-based catalyst
(tetra isopropyl titanate, TIPT) as a catalyst were put in a
3 liter, four-neck reactor equipped with a cooler, a
10 condenser, a decanter, a reflux pump, a temperature
controller, and a stirrer, and the temperature was slowly
increased to about 170°C. The generation of water was
initiated at about 170°C, and an esterification reaction was
conducted for about 4.5 hours while continuously introducing
15 nitrogen gas at a reaction temperature of about 220°C under
an atmospheric pressure condition. The reaction was
terminated when an acid value reached 0.01.
[0084] After the completion of the reaction, distillation
extraction was performed for 0.5 hours to 4 hours under
20 reduced pressure in order to remove unreacted raw materials.
Steam extraction was performed for 0.5 hours to 3 hours under
reduced pressure using steam in order to remove the unreacted
raw materials below a predetermined amount level. A
temperature of a reaction solution was cooled to about 90°C
25 to perform a neutralization treatment using an alkaline
24
solution. In addition, washing may also be performed and
thereafter, water was removed by dehydrating the reaction
solution. Filter media were introduced into the dehydrated
reaction solution and stirred for a predetermined time. Then,
the solution was filtered to finally obtain 1,326.7 5 g (yield:
99.0%) of di-2-ethylhexyl terephthalate.
[0085] Preparation Example 2: Preparation of DINTP
[0086] DINTP was prepared in the same manner as in
10 Preparation Example 1 except that isononyl alcohol was used
instead of using 2-ethylhexyl alcohol during the
esterification reaction.
[0087] Preparation Example 3: Preparation of DOTP/BOTP/DBTP
15 mixture (First Mixture) (GL 500)
[0088] 2,000 g of dioctyl terephthalate obtained in
Preparation Example 1 and 340 g of n-butanol (17 parts by
weight based on 100 parts by weight of the DOTP) were
introduced into a reactor equipped with a stirrer, a
20 condenser, and a decanter, and a transesterification reaction
was carried out at a reaction temperature of 160°C for 2
hours under a nitrogen atmosphere to obtain an ester
plasticizer composition including 4.0 wt% of dibutyl
terephthalate (DBTP), 35.0 wt% of butylisononyl terephthalate
25 (BINTP), and 61.0 wt% of diisononyl terephthalate (DINTP).
25
[0089] Mixed distillation of the reaction product was
conducted to remove butanol and 2-ethylhexyl alcohol and to
finally prepare a first mixture.
[0090] Preparation Example 4: Preparation 5 of
DINTP/OINTP/DOTP mixture (Third Mixture) (GL 100)
[0091] 498.0 g of purified terephthalic acid (TPA), 975 g of
2-ethylhexyl alcohol (2-EH) (molar ratio of TPA:2-EH=1.0:2.5),
216.5 g of isononyl alcohol (INA) (molar ratio of
10 TPA:INA=1.0:0.5), and a titanium-based catalyst (tetra
isopropyl titanate, TIPT) as a catalyst were put in a 3 liter,
four-neck reactor equipped with a cooler, a condenser, a
decanter, a reflux pump, a temperature controller, and a
stirrer, and the temperature was slowly increased to about
15 170°C. The generation of water was initiated at about 170°C,
and an esterification reaction was conducted for about 4.5
hours while continuously introducing nitrogen gas at a
reaction temperature of about 220°C under an atmospheric
pressure condition. The reaction was terminated when an acid
20 value reached 0.01.
[0092] After the completion of the reaction, distillation
extraction was performed for 0.5 hours to 4 hours under
reduced pressure in order to remove unreacted raw materials.
Steam extraction was performed for 0.5 hours to 3 hours under
25 reduced pressure using steam in order to remove the unreacted
26
raw materials below a predetermined amount level. A
temperature of a reaction solution was cooled to about 90°C
to perform a neutralization treatment using an alkaline
solution. In addition, washing may also be performed and
thereafter, water was removed by dehydrating the 5 reaction
solution. Filter media were introduced into the dehydrated
reaction solution and stirred for a predetermined time. Then,
the solution was filtered to finally obtain a third mixture.
10 [0093] Preparation Example 5: Preparation of TBC
[0094] 706 g (yield: 98%) of tributyl citrate was finally
obtained by using 384 g of citric acid and 580 g of butanol
as reaction raw materials.
15 [0095] Preparation Example 6: Preparation of TOC
[0096] 1,029 g (yield: 98%) of tri-2-ethylhexyl citrate was
finally obtained by using 384 g of citric acid and 1,014 g of
2-ethylhexanol as reaction raw materials.
20 [0097] Preparation Example 7: Preparation of TPC
[0098] 796 g (yield: 98%) of tripentyl citrate was finally
obtained by using 384 g of citric acid and 688 g of 1-
pentanol as reaction raw materials.
25 [0099] Preparation Example 8: Preparation of THC
27
[00100] 878 g (yield: 98%) of trihexyl citrate was finally
obtained by using 384 g of citric acid and 797 g of n-hexanol
as reaction raw materials.
[00101] Preparation Example 9: Preparation of 5 TiBC
[00102] 706 g (yield: 98%) of triisobutyl citrate was finally
obtained by using 384 g of citric acid and 580 g of
isobutanol as reaction raw materials.
10 [00103] Preparation Example 10: Preparation of TiNC
[00104] 1,111 g (yield: 98%) of triisobutyl citrate was
finally obtained by using 384 g of citric acid and 1,123 g of
isononanol as reaction raw materials.
15 [00105] Preparation Example 11: Preparation of BOC-A
[00106] A transesterification reaction was carried out by
using 1,000 g of the TOC prepared in Preparation Example 6
and 300 g of n-butanol as reaction raw materials, and 840 g
of butyloctyl citrate was finally obtained. For reference,
20 the product is a composition, wherein main components are BOC
bonded to two butyl groups, BOC bonded to one butyl group,
and TOC not bonded to a butyl group, which were categorized
by the alkyl group bonded to three ester groups of the
citrate compound, and weight ratios of the main components
25 were about 20%, 50%, and 30%, respectively.
28
[00107] Preparation Example 12: Preparation of BOC-B
[00108] A transesterification reaction was carried out by
using 1,000 g of the TOC prepared in Preparation Example 6
and 150 g of n-butanol as reaction raw materials, and 940 5 g
of butyloctyl citrate was finally obtained. For reference,
the product is a composition, wherein main components are BOC
bonded to two butyl groups, BOC bonded to one butyl group,
and TOC not bonded to a butyl group, which were categorized
10 by the alkyl group bonded to three ester groups of the
citrate compound, and weight ratios of the main components
were about 10%, 40%, and 50%, respectively.
[00109] Plasticizer compositions of Examples 1 to 17 were
15 prepared by mixing the materials prepared in Preparation
Examples 1 to 12, and the compositions are summarized in the
following Tables 1 to 5. Physical properties of the
plasticizer compositions were evaluated according to the
following test items.
20 [00110] [Table 1]
Terephthalatebased
material
Citrate-based
material
Mixing weight
ratio
Example 1-1 Preparation
Example 1 (DOTP)
Preparation
Example 5 (TBC) 95:5
Example 1-2
7:3
Example 1-3 5:5
Example 1-4 3:7
29
Example 1-5 1:9
Example 2-1 Preparation
Example 6 (TOC) 95:5
Example 2-2
7:3
Example 2-3 5:5
Example 2-4 3:7
Example 2-5 1:9
Example 3-1 Preparation
Example 7 (TPC) 9:1
Example 3-2
7:3
Example 3-3 5:5
Example 4-1 Preparation
Example 8 (THC) 9:1
Example 4-2
7:3
Example 4-3 5:5
Example 5-1 Preparation
Example 9 (TiBC) 8:2
Example 5-2
6:4
Example 5-3 4:6
Example 5-4 2:8
Example 6-1 Preparation
Example 10 (TiNC) 9:1
Example 6-2
7:3
Example 6-3 5:5
Example 6-4 3:7
Example 6-5 1:9
Example 7-1 Preparation
Example 11 (BOC-A) 85:15
Example 7-2
7:3
Example 7-3 6:4
Example 8-1 Preparation
Example 12 (BOC-B) 85:15
Example 8-2 7:3
30
Example 8-3 6:4
[00111] [Table 2]
Terephthalatebased
material
Citrate-based
material
Mixing weight
ratio
Example 9-1 Preparation
Example 2 (DINTP)
Preparation
Example 5 (TBC) 8:2
Example 9-2
6:4
Example 9-3 4:6
Example 9-4 2:8
Example 10-1 Preparation
Example 6 (TOC) 8:2
Example 10-2
6:4
Example 10-3 4:6
Example 10-4 2:8
Example 11-1 Preparation
Example 9 (TiBC) 8:2
Example 11-2
6:4
Example 11-3 4:6
Example 11-4 2:8
[00112] [Table 3]
Terephthalatebased
material
Citrate-based
material
Mixing weight
ratio
Example 12-1 Preparation
Example 3
Preparation
Example 11 (BOC-A) 85:15
Example 12-2
7:3
Example 12-3 6:4
Example 13-1 Preparation
Example 12 (BOC-B) 85:15
Example 13-2
7:3
Example 13-3 6:4
5
31
[00113] [Table 4]
Terephthalatebased
material
Citrate-based
material
Mixing weight
ratio
Example 14-1 Preparation
Example 4
Preparation
Example 5 (TBC) 95:5
Example 14-2
7:3
Example 14-3 5:5
Example 14-4 1:9
Example 15-1 Preparation
Example 6 (TOC) 7:3
[00114] [Table 5]
Terephthalatebased
material
Citrate-based
material
Epoxidized
oil
Mixing weight
ratio
Example 16-1 Preparation
Example 1 (DOTP)
Preparation
Example 5 (TBC) ESO (3:5):2
Example 16-2
(6:3):1
Example 16-3 (6:2):2
Example 16-4 (5:3):2
Example 16-5 (4:4):2
Example 17-1 Preparation
Example 6 (TOC) (3:3):4
Example 17-2
(4:3):3
Example 17-3 (5:3):2
[00115] 5
[00116] Hardness Measurement
[00117] Shore hardness (3T, 10s) was measured at 25°C in
accordance with ASTM D2240.
10 [00118] Tensile Strength Measurement
32
[00119] A breaking point of a specimen was measured after
pulling the specimen at a cross-head speed of 200 mm/min (1T)
using a test instrument, U.T.M (4466, Instron) by the method
of ASTM D638. The tensile strength was calculated as follows.
[00120] Tensile strength (kgf/mm2) = 5 load value
(kgf)/(thickness (mm) x width (mm))
[00121] Elongation Rate Measurement
[00122] A breaking point of a specimen was measured after
10 pulling the specimen at a cross-head speed of 200 mm/min (1T)
using the U.T.M by the method of ASTM D638, and the
elongation rate was calculated as follows.
[00123] Elongation rate (%) = [length after
elongation/initial length] x 100
15
[00124] Migration Loss Measurement
[00125] A specimen having a thickness of 2 mm or more was
obtained in accordance with KSM-3156. PS plates were
respectively attached on both sides of the specimen, and the
20 weight of 1 kgf/cm2 was then applied thereto. The specimen
was left standing for 72 hours in a hot air circulating oven
(80°C), and cooled at room temperature for 4 hours.
Thereafter, the PS plates attached to the both sides of the
specimen were removed. Then, weights of the specimen before
25 and after being left standing in the oven were measured, and
33
migration loss was calculated by the following equation.
[00126] Migration loss (%) = [(initial weight of a specimen
at room temperature - weight of the specimen after being left
standing in an oven)/initial weight of the specimen at room
temperature] 5 x 100
[00127] Volatile Loss Measurement
[00128] The specimen thus prepared was heated at 80°C for 72
hours, and the weight of the specimen was measured.
10 [00129] Volatile Loss (%) = [(initial weight of a specimen -
weight of the specimen after heating)/initial weight of the
specimen] x 100
[00130] Stress Test
15 [00131] After the specimen, in a state of being bent, was
left standing for a predetermined time at room temperature,
degree of migration was observed and the degree was expressed
as a numerical value. Characteristics were better as the
value was closer to 0.
20
[00132] Light Resistance Measurement
[00133] A specimen was mounted on an accelerated weathering
(QUV) apparatus and irradiated with ultraviolet (UV) light
for 200 hours by the method of ASTM 4329-13, and changes in
25 color were then calculated by using a reflectometer.
34
[00134] Heat Resistance Measurement
[00135] A degree of discoloration of the initial specimen
according to the volatile loss measurement method and the
specimen after the volatile loss test was measured. T5 he
measurement value was determined by changes in E value with
respect to L,a,b values using a colorimeter.
[00136] Experimental Example 1: DOTP-based Plasticizer
10 Compositions
[00137] 1. Mixed Plasticizer Composition of DOTP and TBC
[00138] DOTP and TBC were mixed in mixing ratios of Examples
1-1 to 1-5 listed in Table 1 to obtain mixed plasticizer
compositions, and the compositions were used as experimental
15 specimens.
[00139] With reference to ASTM D638, the specimens were
prepared in such a manner that 40 parts by weight of the
mixed plasticizer composition, 2.5 parts by weight of an
auxiliary stabilizer (ESO), and 3 parts by weight of a
20 stabilizer (LOX-430) were mixed with 100 parts by weight of
PVC in a 3 L super mixer at 700 rpm and a temperature of 98°C,
a 5 mm thick sheet was prepared by using a roll mill at 160°C
for 4 minutes, and a sheet having a thickness of 1 mm to 3 mm
was then prepared by low-pressure pressing for 2.5 minutes
25 and high-pressure pressing for 2 minutes at a temperature of
35
180°C. Physical properties of each specimen were evaluated
for the above-described test items, and the results thereof
are summarized in Table 6 below.
[00140] [Table 6]
Plastici
zer
Hardness
(Shore
“A”)
Tensile
strength
(Kg/cm2)
Elongati
on rate
(%)
Migratio
n loss
(%)
Volatile
loss (%)
Light
resistan
ce (E)
Absorpti
on time
(sec)
Stress
test
(24hrs)
Example
1-1 95:5 86.5 222.6 321.7 0.20 2.32 2.14 392 0.5
Example
1-2 7:3 86.0 221.3 315.5 0.23 2.88 1.76 372 0.5
Example
1-3 5:5 84.8 216.5 313.2 0.24 2.90 1.35 341 0.5
Example
1-4 3:7 83.9 198.3 280.2 2.21 11.01 1.22 235 0.5
Example
1-5 1:9 83.1 190.3 278.5 2.45 12.31 1.19 214 0.5
Compara
tive
Example
1
DOP 88.2 203.4 289.6 3.56 6.64 1.13 408 1.0
Compara
tive
Example
2
DOTP 89.4 222.1 324.9 0.25 2.75 2.71 465 3.0
5
[00141] As illustrated in Table 6, when Examples 1-1 to 1-5
and Comparative Examples 1 and 2 using DOP and DOTP
plasticizers, as commercial products widely sold, were
compared, it may be confirmed that Examples 1-1 to 1-5 had
10 all physical properties, such as hardness, absorption time,
tensile strength, elongation rate, stress resistance, and
migration, equal to or better than Comparative Examples 1 and
2. Furthermore, it may be understood that Examples 1-1 to 1-
5 improved poor physical properties of the conventional
15 plasticizer products.
36
[00142] In a case in which the absorption time of the
plasticizer was short, processability may be improved.
However, since limitations due to gelling may occur during
processing even in the case that the absorption time is
excessively 5 short, an appropriate absorption time may need to
be maintained. From this point of view, with respect to
Examples 1-4 and 1-5 in which an excessive amount of TBC was
mixed, the absorption time seemed to be relatively short, and
thus, there is a possibility that the limitations due to
10 gelling may occur during processing when the plasticizer
composition was used. However, with respect to Examples 1-1
to 1-3 in which the amount of TBC was appropriately adjusted,
since absorption was performed for an appropriate period of
time, it was confirmed that the limitations did not occur.
15 Furthermore, it may be confirmed that a difference in the
physical properties, such as volatile loss, was large
according to the adjustment of the mixing ratio. Thus, it
may be understood that a better plasticizer composition may
be obtained when the mixing ratio was appropriately adjusted.
20
[00143] 2. Mixed Plasticizer Composition of DOTP and TOC
[00144] DOTP and TOC were mixed in mixing ratios of Examples
2-1 to 2-5 listed in Table 1 to obtain mixed plasticizer
compositions, and the compositions were used as experimental
25 specimens. The preparation of the specimens and physical
37
property evaluation were performed in the same manner as in
[1. Mixed Plasticizer Composition of DOTP and TBC], and the
results thereof are presented in Table 7 below.
[00145] [Table 7]
Plastici
zer
Hardness
(Shore
“A”)
Tensile
strength
(Kg/cm2)
Elongati
on rate
(%)
Migratio
n loss
(%)
Volatile
loss (%)
Light
resistan
ce (E)
Absorpti
on time
(sec)
Stress
test
(24hrs)
Example
2-1 95:5 89.4 230.8 326.8 0.15 0.77 2.23 450 0.5
Example
2-2 7:3 89.5 231.6 328.1 0.13 0.60 1.90 475 0
Example
2-3 5:5 89.7 235.9 332.5 0.10 0.32 1.45 482 0
Example
2-4 3:7 91.2 235.5 340.2 0.11 0.31 1.33 586 0
Example
2-5 1:9 91.6 237.0 342.1 0.10 0.28 1.18 604 0
Compara
tive
Example
1
DOP 88.4 205.8 282.3 3.77 6.80 1.13 420 1.0
Compara
tive
Example
2
DOTP 89.4 226.0 320.0 0.23 2.05 2.71 445 3.0
5
[00146] As illustrated in Table 7, when Examples 2-1 to 2-5
and Comparative Examples 1 and 2 using DOP and DOTP
plasticizers, as commercial products widely sold, were
compared, it may be confirmed that Examples 2-1 to 2-5 had
10 all physical properties equal to or better than the
conventional DOTP product. Furthermore, it may be understood
that Examples 2-1 to 2-5 improved poor physical properties of
the conventional plasticizer products.
[00147] With respect to the absorption time, it may be
15 understood that Examples 2-1 to 2-3 had an appropriate
38
absorption time, but Examples 2-4 and 2-5 required a
relatively long absorption time. Since this may cause the
deterioration of processability and productivity, it may also
be confirmed that, in some cases, it needs to be careful when
5 an excessive amount of TOC was mixed.
[00148] 3. Mixed Plasticizer Composition of DOTP and TPC
[00149] DOTP and tripentyl citrate (TPC) or triamyl citrate
were mixed in mixing ratios of Examples 3-1 to 3-3 listed in
10 Table 1 to obtain mixed plasticizer compositions, and the
compositions were used as experimental specimens. The
specimens were prepared in the same manner as in [1. Mixed
Plasticizer Composition of DOTP and TBC] except that a
stabilizer, BZ153T, was used during the formulation of the
15 sheet, physical properties were similarly evaluated, and the
results thereof are presented in Table 8 below.
[00150] [Table 8]
Plasticiz
er
Hardness
(Shore
“A”)
Tensile
strength
(Kg/cm2)
Elongation
rate (%)
Migration
loss (%)
Volatile
loss (%)
Light
resistance
(E)
Stress
test
(7 days)
Example
3-1 9:1 90.6 225.3 326.1 1.57 0.70 2.30 1.0
Example
3-2 7:3 89.8 223.4 324.9 1.37 0.92 1.68 0
Example
3-3 5:5 88.7 220.0 320.4 1.09 1.08 1.12 0
Compara
tive
Example
1
DOP 88.4 205.8 282.3 3.77 6.80 1.13 1.0
Compara
tive
Example
2
DOTP 91.8 226.3 318.2 1.65 0.76 2.56 2.0
39
[00151] As illustrated in Table 8, when Examples 3-1 to 3-3
and Comparative Examples 1 and 2 using DOP and DOTP
plasticizers, as commercial products widely sold, were
compared, it may be confirmed that Examples 3-1 to 3-3 5 had
all physical properties equal to or better than the
conventional DOTP product. Furthermore, it may be understood
that Examples 3-1 to 3-3 improved poor physical properties of
the conventional plasticizer products.
10
[00152] 4. Mixed Plasticizer Composition of DOTP and THC
[00153] DOTP and trihexyl citrate (THC) were mixed in mixing
ratios of Examples 4-1 to 4-3 listed in Table 1 to obtain
mixed plasticizer compositions, and the compositions were
15 used as experimental specimens. The specimens were prepared
in the same manner as in [1. Mixed Plasticizer Composition of
DOTP and TBC] except that a stabilizer, BZ153T, was used
during the formulation of the sheet, physical properties were
similarly evaluated, and the results thereof are presented in
20 Table 9 below.
[00154] [Table 9]
Plasticiz
er
Hardness
(Shore
“A”)
Tensile
strength
(Kg/cm2)
Elongation
rate (%)
Migration
loss (%)
Volatile
loss (%)
Light
resistance
(E)
Stress
test
(7 days)
Example
4-1 9:1 91.1 221.9 319.8 0.98 0.69 2.35 1.0
Example
4-2 7:3 90.4 217.4 315.1 0.75 0.74 1.77 1.0
Example 5:5 89.9 210.6 311.5 0.62 0.73 1.23 0.5
40
4-3
Compara
tive
Example
1
DOP 88.4 205.8 282.3 3.77 6.80 1.13 1.0
Compara
tive
Example
2
DOTP 91.8 226.3 318.2 1.65 0.76 2.56 2.0
[00155] As illustrated in Table 9, when Examples 4-1 to 4-3
and Comparative Examples 1 and 2 using DOP and DOTP
plasticizers, as commercial products widely sold, were
compared, it may be confirmed that Examples 4-1 to 4-5 3 had
all physical properties equal to or better than the
conventional DOTP product. Furthermore, it may be understood
that Examples 4-1 to 4-3 improved poor physical properties of
the conventional plasticizer products.
10
[00156] 5. Mixed Plasticizer Composition of DOTP and TiBC
[00157] DOTP and triisobutyl citrate (TiBC) were mixed in
mixing ratios of Examples 5-1 to 5-4 listed in Table 1 to
obtain mixed plasticizer compositions, and the compositions
15 were used as experimental specimens. The preparation of the
specimens and physical property evaluation were performed in
the same manner as in [1. Mixed Plasticizer Composition of
DOTP and TBC] except that the working temperature during the
evaluation of the volatile loss was set to 100°C, and the
20 results thereof are presented in Table 10 below.
41
[00158] [Table 10]
Plasticizer Hardness
(Shore “A”)
Tensile
strength
(Kg/cm2)
Elongation
rate (%)
Migration
loss (%)
Volatile
loss (%)
Example 5-1 8:2 86.0 228.6 311.2 0.82 2.35
Example 5-2 6:4 85.4 221.3 308.5 1.02 4.62
Example 5-3 4:6 84.0 217.9 302.5 1.37 6.88
Example 5-4 2:8 83.0 211.6 294.6 1.88 7.85
Comparative
Example 2 DOTP 89.6 230.7 315.7 0.70 0.84
Comparative
Example 3 TiBC 82.5 200.3 282.5 3.56 11.57
[00159] As illustrated in Table 10, when Examples 5-1 to 5-4
and Comparative Example 2 using a DOTP plasticizer, as a
commercial product widely sold, were compared, it 5 t may be
confirmed that Examples 5-1 to 5-4 had all physical
properties equal to or better than the conventional DOTP
product. Furthermore, it may be understood that Examples 5-1
to 5-4 improved poor physical properties of the conventional
10 plasticizer product.
[00160] With respect to Examples 5-3 and 5-4 in which a
relatively excessive amount of TiBC was included in
comparison to Examples 5-1 and 5-2, it may be confirmed that
tensile strength and elongation rate were reduced and
15 migration loss and volatile loss were significantly reduced.
That is, it may also be confirmed that, in some cases, it
needs to be careful when an excessive amount of TiBC was
mixed.
42
[00161] 6. Mixed Plasticizer Composition of DOTP and TiNC
[00162] DOTP and triisononyl citrate (TiNC) were mixed in
mixing ratios of Examples 6-1 to 6-5 listed in Table 1 to
obtain mixed plasticizer compositions, and the 5 compositions
were used as experimental specimens. The specimens were
prepared in the same manner as in [1. Mixed Plasticizer
Composition of DOTP and TBC] except that a stabilizer, BZ153T,
was used during the formulation of the sheet, physical
10 properties were similarly evaluated, and the results thereof
are presented in Table 11 below.
[00163] [Table 11]
Plasticizer
Hardness
(Shore
“A”)
Tensile
strength
(Kg/cm2)
Elongation
rate (%)
Migration
loss (%)
Volatile
loss (%)
Light
resistance
(E)
Example 6-1 9:1 92.2 238.0 326.9 1.04 0.56 1.95
Example 6-2 7:3 92.5 244.8 335.5 0.85 0.48 1.68
Example 6-3 5:5 92.8 249.2 346.6 0.62 0.42 1.39
Example 6-4 3:7 94.1 257.5 360.3 0.54 0.50 1.02
Example 6-5 1:9 94.8 261.4 369.3 0.58 0.43 0.88
Comparative
Example 2 DOTP 92.0 227.5 315.1 1.51 0.79 2.71
[00164] As illustrated in Table 11, when Examples 6-1 to 6-4
15 and Comparative Example 2 using a DOTP plasticizer, as a
commercial product widely sold, were compared, it may be
confirmed that Examples 6-1 to 6-4 had all physical
properties equal to or better than the conventional DOTP
43
product. Furthermore, it may be understood that Examples 6-1
to 6-4 improved poor physical properties of the conventional
plasticizer product.
[00165] With respect to Examples 6-3 and 6-4 in which a
relatively excessive amount of TiNC was 5 included in
comparison to Examples 6-1 and 6-2, it may be confirmed that
plasticizing efficiency was reduced as hardness was
significantly increased. That is, it may also be confirmed
that, in some cases, it needs to be careful when an excessive
10 amount of TiNC was mixed.
[00166] 7. Mixed Plasticizer Composition of DOTP and BOC
[00167] DOTP and butyloctyl citrate (BOC) were mixed in
mixing ratios of Examples 7-1 to 7-3 (BOC-A) and Examples 8-1
15 to 8-3 (BOC-B) listed in Table 1 to obtain mixed plasticizer
compositions, and the compositions were used as experimental
specimens. The specimens were prepared in the same manner as
in [1. Mixed Plasticizer Composition of DOTP and TBC] except
that a stabilizer, BZ153T, was used during the formulation of
20 the sheet, physical properties were similarly evaluated, and
the results thereof are presented in Table 12 below.
[00168] [Table 12]
Plasticizer Hardness
(Shore “A”)
Tensile
strength
(Kg/cm2)
Elongation
rate (%)
Migration
loss (%)
Volatile
loss (%)
Example 7-1 85:15 88.3 228.0 334.7 0.22 0.85
44
Example 7-2 7:3 88.0 222.6 331.6 0.18 0.42
Example 7-3 6:4 87.9 225.5 336.4 0.15 0.35
Example 8-1 85:15 88.2 222.8 332.7 0.20 0.59
Example 8-2 7:3 88.7 225.8 338.6 0.16 0.46
Example 8-3 6:4 89.8 229.7 339.4 0.12 0.32
Comparative
Example 2 DOTP 89.5 228.8 318.1 0.24 1.08
[00169] As illustrated in Table 12, when Examples 7-1 to 7-3,
Examples 8-1 to 8-3, and Comparative Example 2 using a DOTP
plasticizer, as a commercial product widely sold, were
compared, it may be confirmed that Examples 7-1 to 7-5 3 and
Examples 8-1 to 8-3 had all physical properties equal to or
better than the conventional DOTP product. In particular, it
may be understood that elongation rate and volatile loss
characteristics were significantly improved.
10
[00170] Experimental Example 2: DINTP-based Plasticizer
Compositions
[00171] 1. Mixed Plasticizer Composition of DINTP and TBC
[00172] DINTP and tributyl citrate (TBC) were mixed in mixing
15 ratios of Examples 9-1 to 9-4 listed in Table 2 to obtain
mixed plasticizer compositions, and the compositions were
used as experimental specimens. The specimens were prepared
in the same manner as in [1. Mixed Plasticizer Composition of
DOTP and TBC] except that a stabilizer, BZ153T, was used
45
during the formulation of the sheet, physical properties were
similarly evaluated, and the results thereof are presented in
Table 13 below.
[00173] [Table 13]
Plasticiz
er
Hardness
(Shore
“A”)
Tensile
strength
(Kg/cm2)
Elongation
rate (%)
Migration
loss (%)
Volatile
loss (%)
Light
resistance
(E)
Stress
test
(24 hrs)
Example
9-1 8:2 91.0 232.1 342.0 2.38 1.03 1.74 1.5
Example
9-2 6:4 89.3 232.8 335.7 2.30 1.23 1.56 1.0
Example
9-3 4:6 87.7 225.0 316.2 2.30 1.88 1.31 0.5
Example
9-4 2:8 87.0 215.3 317.2 2.39 2.56 1.30 0.5
Compara
tive
Example
4
DINTP 92.7 230.2 314.4 2.72 0.89 3.56 2.5
Compara
tive
Example
5
TBC 86.3 202.4 301.4 6.99 15.38 1.33 0
5
[00174] As illustrated in Table 13, when Examples 9-1 to 9-4,
Comparative Example 4 using a DINTP plasticizer, as a
commercial product widely sold, and Comparative Example 5, in
which a terephthalate-based material was not included, were
10 compared, it may be confirmed that Examples 9-1 to 9-4 had
all physical properties equal to or better than the
conventional DINTP product. Furthermore, it may be
understood that Examples 9-1 to 9-4 improved poor physical
properties of the conventional plasticizer products.
15 [00175] With respect to Examples 9-3 and 9-4 in which a
relatively excessive amount of TBC was included in comparison
46
to Examples 9-1 and 9-2, it may be confirmed that effects of
improving tensile strength and elongation rate were
insignificant. That is, it may also be confirmed that, in
some cases, it needs to be careful when an excessive amount
of TBC 5 was mixed.
[00176] 2. Mixed Plasticizer Composition of DINTP and TOC
[00177] DINTP and trioctyl citrate (TOC) were mixed in mixing
ratios of Examples 10-1 to 10-4 listed in Table 2 to obtain
10 mixed plasticizer compositions, and the compositions were
used as experimental specimens. The specimens were prepared
in the same manner as in [1. Mixed Plasticizer Composition of
DOTP and TBC] except that a stabilizer, BZ153T, was used
during the formulation of the sheet and the working
15 temperature during the evaluation of the volatile loss was
set to 100°C, and the results thereof are presented in Table
14 below.
[00178] [Table 14]
Plasticiz
er
Hardness
(Shore
“A”)
Tensile
strength
(Kg/cm2)
Elongation
rate (%)
Migration
loss (%)
Volatile
loss (%)
Light
resistance
(E)
Stress
test
(24 hrs)
Example
10-1 8:2 92.0 231.9 374.5 1.82 0.83 1.89 1.5
Example
10-2 6:4 91.7 229.8 369.9 1.61 0.81 1.75 1.0
Example
10-3 4:6 91.5 228.1 370.3 1.41 0.80 1.45 0.5
Example
10-4 2:8 91.3 230.2 373.4 1.24 0.81 1.46 0.5
Compara
tive
Example
4
DINTP 92.3 217.0 341.3 2.82 1.36 3.56 2.0
47
Compara
tive
Example
6
TOC 91.3 230.1 369.0 0.82 0.82 1.35 0.5
[00179] As illustrated in Table 14, when Examples 10-1 to 10-
4, Comparative Example 4 using a DINTP plasticizer, as a
commercial product widely sold, and Comparative Example 6, in
which a terephthalate-based material was not included, 5 , were
compared, it may be confirmed that Examples 10-1 to 10-4 had
all physical properties equal to or better than the
conventional DINTP product. Furthermore, it may be
understood that Examples 10-1 to 10-4 improved poor physical
10 properties of the conventional plasticizer product.
[00180] 3. Mixed Plasticizer Composition of DINTP and TiBC
[00181] DINTP and triisobutyl citrate (TiBC) were mixed in
mixing ratios of Examples 11-1 to 11-4 listed in Table 2 to
15 obtain mixed plasticizer compositions, and the compositions
were used as experimental specimens. The specimens were
prepared in the same manner as in [1. Mixed Plasticizer
Composition of DOTP and TBC] except that a stabilizer, BZ153T,
was used during the formulation of the sheet and the working
20 temperature during the evaluation of the volatile loss was
set to 100°C, and the results thereof are presented in Table
15 below.
[00182] [Table 15]
48
Plasticizer
Hardness
(Shore
“A”)
Tensile
strength
(Kg/cm2)
Elongation
rate (%)
Migration
loss (%)
Volatile
loss (%)
Light
resistance
(E)
Example 11-1 8:2 90.8 236.1 348.5 2.12 1.83 1.82
Example 11-2 6:4 89.5 237.5 332.8 2.00 2.11 1.46
Example 11-3 4:6 87.3 228.9 320.9 2.86 2.59 1.25
Example 11-4 2:8 87.1 221.0 315.1 3.26 3.44 1.11
Comparative
Example 4 DINTP 92.5 235.7 318.7 2.99 0.89 3.56
Comparative
Example 7 TiBC 86.0 210.3 296.7 7.56 14.23 1.09
[00183] As illustrated in Table 15, when Examples 11-1 to 11-
4, Comparative Example 4 using a DINTP plasticizer, as a
commercial product widely sold, and Comparative Example 7, in
which a terephthalate-based material was not included, 5 , were
compared, it may be confirmed that Examples 11-1 to 11-4 had
all physical properties equal to or better than the
conventional DINTP product. Furthermore, it may be
understood that Examples 11-1 to 11-4 improved poor physical
10 properties of the conventional plasticizer products.
[00184] With respect to Examples 11-3 and 11-4 in which a
relatively excessive amount of TiBC was included in
comparison to Examples 11-1 and 11-2, it may be confirmed
that effects of improving tensile strength and elongation
15 rate characteristics were insignificant. That is, it may
also be confirmed that, in some cases, it needs to be careful
when an excessive amount of TiBC was mixed.
49
[00185] Experimental Example 3: Mixed Plasticizer
Compositions of First Mixture and BOC
[00186] The first mixture (DOTP/BOTP/DBTP) of Preparation
Example 3 and butyloctyl citrate (BOC) were mixed in mixing
ratios of Examples 12-1 to 12-3 (BOC-A) and Examples 13-1 5 to
13-3 (BOC-B) listed in Table 3 to obtain mixed plasticizer
compositions, and the compositions were used as experimental
specimens. The specimens were prepared in the same manner as
in [1. Mixed Plasticizer Composition of DOTP and TBC] except
10 that 50 parts by weight of the mixed plasticizer composition
was added, an auxiliary stabilizer (ESO) was not added, and a
stabilizer, BZ153T, was used during the formulation of the
sheet, physical properties were similarly evaluated, and the
results thereof are presented in Tables 16 and 17 below.
15 [00187] [Table 16]
Plasticizer Hardness
(Shore “A”)
Tensile
strength
(Kg/cm2)
Elongation
rate (%)
Migration
loss (%)
Volatile
loss (%)
Example 12-1 85:15 82.3 208.04 344.68 3.94 1.62
Example 12-2 7:3 81.0 202.56 341.64 3.69 1.42
Example 12-3 6:4 80.9 205.51 346.35 3.21 1.28
Example 13-1 85:15 81.2 202.84 342.71 3.71 1.59
Example 13-2 7:3 81.7 205.76 348.63 3.32 1.36
Example 13-3 6:4 82.8 209.66 348.12 2.90 1.19
Comparative
Example 8
First
mixture 81.8 212.82 349.42 4.24 1.79
[00188] [Table 17]
50
Stress test 24 hours 72 hours 168 hours
Example 12-1 1.0 1.5 2.0
Example 12-2 1.0 0.5 2.0
Example 12-3 0.5 1.0 1.5
Example 13-1 1.0 1.5 2.0
Example 13-2 1.0 1.0 1.5
Example 13-3 1.0 1.5 1.5
Comparative Example
8 1.5 2.0 2.5
[00189] As illustrated in Tables 16 and 17, when Examples 12-
1 to 12-3, Examples 13-1 to 13-3, and Comparative Example 8
using the mixed plasticizer composition, as a mixed
composition 5 of DOTP, BOTP, and DBTP, were compared, it may be
confirmed that Examples 12-1 to 12-3 and Examples 13-1 to 13-
3 had all physical properties equal to or better than the
conventional product.
10 [00190] Experimental Example 4: Mixed Plasticizer
Compositions of Third Mixture and TBC or TOC
[00191] The third mixture (DINTP/OINTP/DOTP) of Preparation
Example 4 and tributyl citrate (TBC) or trioctyl citrate
(TOC) were mixed in mixing ratios of Examples 14-1 to 14-4
15 and Example 15-1 listed in Table 4 to obtain mixed
plasticizer compositions, and the compositions were used as
experimental specimens. The preparation of the specimens and
physical property evaluation were performed in the same
51
manner as before, and the results thereof are presented in
Tables 18 and 19 below.
[00192] [Table 18]
Plasticizer
Hardness
(Shore
“A”)
Tensile
strength
(Kg/cm2)
Elongation
rate (%)
Migration
loss (%)
Volatile
loss (%)
Light
resistance
(E)
Example 14-1 95:5 92.0 254.5 308.2 1.90 0.73 3.21
Example 14-2 7:3 91.1 246.0 303.6 1.71 0.85 2.85
Example 14-3 5:5 88.2 241.0 297.0 1.63 0.93 2.12
Example 14-4 1:9 86.5 216.3 264.6 1.68 2.12 2.01
Example 15-1 7:3 92.5 257.5 299.3 1.48 0.65 2.94
Comparative
Example 2 DOTP 91.6 246.4 296.6 1.68 0.72 5.67
Comparative
Example 9
Third
mixture 92.8 254.4 309.0 2.03 0.72 5.23
[00193] [5 Table 19]
Stress test 24 hours 72 hours 168 hours
Example 14-1 0.5 1.5 1.5
Example 14-2 0 0.5 1.0
Example 14-3 0 0.5 0
Example 14-4 0 0 0
Example 15-1 0.5 1.0 1.5
Comparative Example
2 0.5 1.0 1.5
Comparative Example
9 0.5 1.5 1.5
[00194] As illustrated in Tables 18 and 19, when Examples 14-
1 to 14-4, Example 15-1, and Comparative Example 9 using the
mixed plasticizer composition, as a mixed composition of
52
DINTP, OINTP, and DOTP, were compared, it may be confirmed
that Examples 14-1 to 14-4 and Example 15-1 had all physical
properties equal to or better than the conventional product.
[00195] With respect to Example 14-4 in which a relatively
excessive amount of TBC was included in comparison 5 to
Examples 14-1 to 14-3, it may be confirmed that tensile
strength and elongation rate characteristics were reduced and
volatile loss was also poor. That is, it may also be
confirmed that, in some cases, it needs to be careful when an
10 excessive amount of TBC was mixed.
[00196] Experimental Example 5: Mixed Plasticizer
Compositions of DOTP, TBC, and Epoxidized Oil
[00197] 1. Mixed Plasticizer Composition of DOTP, TBC, and
15 ESO
[00198] DOTP, TBC, and ESO were mixed in mixing ratios of
Examples 16-1 to 16-5 listed in Table 5 to obtain mixed
plasticizer compositions, and the compositions were used as
experimental specimens. The specimens were prepared in the
20 same manner as in [1. Mixed Plasticizer Composition of DOTP
and TBC] except that 30 parts by weight of the mixed
plasticizer composition was added, an auxiliary stabilizer
(ESO) was not added, and 0.5 part by weight of titanium
dioxide (TiO2) was additionally used during the formulation
25 of the sheet, physical properties were similarly evaluated
53
and the results thereof are presented in Table 20 below, and
the results of the heat resistance test are presented in FIGS.
1 and 2.
[00199] [Table 20]
Plasticizer Hardness
(Shore “A”)
Tensile
strength
(Kg/cm2)
Elongation
rate (%)
Migration
loss (%)
Volatile
loss (%)
Example 1-2 7:3 94.2 246.7 300.8 0.92 1.57
Example 16-1 3:5:2 93.0 247.8 313.9 0.59 1.55
Example 16-2 6:3:1 94.0 252.5 322.3 0.68 1.14
Example 16-3 6:2:2 94.3 252.5 322.2 0.62 0.80
Example 16-4 5:3:2 94.0 247.9 310.1 0.64 1.00
Example 16-5 4:4:2 93.5 243.2 316.4 0.53 1.17
Comparative
Example 2 DOTP 95.5 268.5 311.0 0.78 0.61
5
[00200] As illustrated in Table 20, when Examples 16-1 to 16-
5 and Comparative Example 2, the DOTP plasticizer composition
as a conventionally used product, were compared, it may be
confirmed that the plasticizer compositions of the examples
10 had properties equal to or better than the conventional
product.
[00201] Referring to images of FIGS. 1 and 2 as the results
of the heat resistance test, it may be confirmed that since
Example 1-2, in which epoxidized oil was not added, was
15 vulnerable to heat, it was blackened. However, it may be
confirmed that there was no change when a predetermined
amount of the epoxidized oil was added. That is, in a case
54
in which a Citrate-based material was added to improve
physical properties of DOTP as a conventional product, it may
be confirmed that heat resistance characteristics may be
relatively poor, but even the heat resistance was also
maintained and improved when the epoxidized oil was added a5 t
the same time.
[00202] 2. Mixed Plasticizer Composition of DOTP, TOC, and
ESO
10 [00203] DOTP, TOC, and ESO were mixed in mixing ratios of
Examples 17-1 to 17-3 listed in Table 5 to obtain mixed
plasticizer compositions, and the compositions were used as
experimental specimens.
[00204] With reference to ASTM D638, the specimens were
15 prepared in such a manner that 50 parts by weight of the
mixed plasticizer composition, 40 parts by weight of a filler
(OMYA1T), 5 parts by weight of a stabilizer (RUP-144), and
0.3 part by weight of a lubricant (St-A) were mixed with 100
parts by weight of PVC in a 3 L super mixer at 700 rpm and a
20 temperature of 98°C, a 5 mm thick sheet was prepared by using
a roll mill at 160°C for 4 minutes, and a sheet having a
thickness of 1 mm to 3 mm was then prepared by low-pressure
pressing for 2.5 minutes and high-pressure pressing for 2
minutes at a temperature of 180°C.
25 [00205] Physical properties of each specimen were evaluated
55
for the above-described test items, and the specimens were
evaluated in the same manner as in [1. Mixed Plasticizer
Composition of DOTP and TBC] except that the working
temperature was set to 121ºC and the evaluation was carried
out for 168 hours during the volatile loss measurement. 5 The
following items were additionally evaluated and the results
thereof are presented in Tables 21 and 22 below, and the
results of the heat resistance test are presented in FIG. 3.
10 [00206]
[00207] Residual Tensile Strength
[00208] The measurement was performed in the same manner as
the above-described tensile strength measurement, and
specimens exposed at 121ºC for 168 hours were used.
15
[00209] Residual Elongation
[00210] The measurement was performed in the same manner as
the above-described elongation rate measurement, and
specimens exposed at 121ºC for 168 hours were used.
20
[00211] Low temperature Resistance
[00212] Five prepared specimens were left standing at a
specific temperature for 3 minutes and were then hit. The
temperature was measured when three out of the five specimens
25 were broken.
56
[00213] [Table 21]
Plastici
zer
Hardness
(Shore
“A”)
Tensile
strength
(Kg/cm2)
Residual
tensile
strength
(%)
Elongati
on rate
(%)
Residual
elongati
on (%)
Migratio
n loss
(%)
Volatile
loss (%)
Low
temperat
ure
resistan
ce (ºC)
Heat
resistan
ce (E)
Example
17-1 3:3:4 86.8 184.3 96.4 292.6 89.5 0.48 8.63 -24.0 35.53
Example
17-2 4:3:3 87.0 185.3 96.5 297.8 92.5 0.63 7.04 -24.5 31.46
Example
17-3 5:3:2 86.8 183.0 103.7 314.8 93.9 0.91 7.06 -26.0 51.13
Compara
tive
Example
10
DIDP 87.5 175.6 94.5 317.9 91.3 0.99 8.36 -25.5 49.18
Compara
tive
Example
11
DINIP 88.0 181.3 94.9 310.2 89.5 1.60 10.49 -28.5 47.02
[00214] As illustrated in Table 21, when Examples 17-1 to 17-
3 and Comparative Examples 10 and 11, the DIDP and DINIP
plasticizer compositions as conventionally used 5 products,
were compared, it may be confirmed that the plasticizer
compositions of the examples had properties equal to or
better than the conventional products. In particular, it may
be confirmed that low temperature resistance properties were
10 almost the same as those of the conventional products, but
heat resistance properties were significantly improved.
[00215] Referring to an image of FIG. 3 as the results of the
thermal stability test, it may be confirmed that since
Comparative Examples 10 and 11, as the conventional products,
15 were vulnerable to heat, Comparative Examples 10 and 11 were
blackened. However, it may be confirmed that there was no
change when a predetermined amount of epoxidized oil was
57
added. That is, in a case in which the epoxidized oil as
well as a Citrate-based material was added to improve
physical properties of the conventional plasticizer products
such as DIDP and DINIP, it was confirmed that even the
thermal stability may also be 5 maintained and improved.
[00216] Experimental Example 6: Comparison to Acetyl Citratebased
material
[00217] In order to compare differences in physical
10 properties between a case, in which an acetyl group was
included in the Citrate-based material, and a case in which
an acetyl group was not included in the Citrate-based
material, Examples 1-2, 2-2, and 5-2 and Comparative Example
12, a plasticizer composition in which acetyl 2-ethylhexyl
15 citrate and DOTP were mixed, were used as experimental
specimens. The preparation of the specimens and physical
property evaluation were performed in the same manner as in
[1. Mixed Plasticizer Composition of DOTP and TBC], and the
results thereof are presented in Table 22 below.
20 [00218] [Table 22]
Plasticizer Hardness
(Shore “A”)
Tensile
strength
(Kg/cm2)
Elongation
rate (%)
Migration
loss (%)
Volatile
loss (%)
Example 1-2 DOTP+TBC
(70:30) 86.0 221.3 315.5 0.23 2.88
Example 2-2 DOTP+TOC
(70:30) 89.5 231.6 328.1 0.13 0.60
Example 5-2 DOTP+TiBC
(60:40) 85.4 221.3 308.5 1.02 4.62
58
Comparative
Example 12
DOTP+ATOC
(70:30) 91.2 237.9 284.6 0.25 0.54
[00219] As illustrated in Table 22, in a case in which acetyl
2-ethylhexyl citrate was mixed and used, it may be confirmed
that since hardness was significantly increased, plasticizing
efficiency, as a physical property highly required 5 for a
plasticizer product, may be deteriorated and elongation rate
characteristics were also reduced. Accordingly, since
economic and process losses may secondarily occur due to the
fact that more plasticizer was needed in comparison to other
10 products, it may be understood that, in some cases, it may
adversely affect the quality of the product according to the
presence of the acetyl group.
[00220] Although the exemplary embodiments of the present
invention have been described in detail, the scope of the
15 present invention is not limited thereto but various
modifications and improvements made by those skilled in the
art using the basic concept of the present invention defined
in the claims also fall within the scope of the present
invention.
20
59
CLAIMS
1. A plasticizer composition comprising:
a terephthalate-based material; and
a Citrate-5 based material,
wherein a weight ratio of the terephthalate-based
material to the Citrate-based material is in a range of 99:1
to 1:99.
10 2. The plasticizer composition of claim 1, wherein the
weight ratio of the terephthalate-based material to the
Citrate-based material is in a range of 95:5 to 50:50.
3. The plasticizer composition of claim 2, wherein the
15 weight ratio of the terephthalate-based material to the
Citrate-based material is in a range of 95:5 to 60:40.
4. The plasticizer composition of claim 1, wherein the
terephthalate-based material comprises a single compound
20 selected from the group consisting of di(2-
ethylhexyl)terephthalate (DEHTP or DOTP), diisononyl
terephthalate (DINTP), dibutyl terephthalate (DBTP), butyl
isononyl terephthalate (BINTP), butyl(2-
ethylhexyl)terephthalate (BEHTP or BOTP), and (2-
25 ethylhexyl)isononyl terephthalate (EHINTP or OINTP), or a
60
mixture in which one or more compounds are mixed.
5. The plasticizer composition of claim 4, wherein the
single compound is di(2-ethylhexyl)terephthalate or
diisononyl 5 terephthalate.
6. The plasticizer composition of claim 4, wherein the
mixture is a first mixture in which di(2-
ethylhexyl)terephthalate, butyl(2-ethylhexyl)terephthalate,
10 and dibutyl terephthalate are mixed,
a second mixture in which diisononyl terephthalate,
butyl isononyl terephthalate, and dibutyl terephthalate are
mixed, or
a third mixture in which di(2-ethylhexyl)terephthalate,
15 (2-ethylhexyl)isononyl terephthalate, and diisononyl
terephthalate are mixed.
7. The plasticizer composition of claim 6, wherein the
first mixture comprises:
20 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.
25 8. The plasticizer composition of claim 6, wherein the
61
second mixture comprises:
3.0 mol% to 99.0 mol% of diisononyl terephthalate;
0.5 mol% to 96.5 mol% of butyl isononyl terephthalate;
and
0.5 mol% to 96.5 mol% of dibutyl terephthalate5 .
9. The plasticizer composition of claim 6, wherein the
third mixture comprises:
3.0 mol% to 99.0 mol% of di(2-ethylhexyl)terephthalate;
10 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 plasticizer composition of claim 1, wherein the
15 Citrate-based material comprises any one selected from the
group consisting of a hybrid alkyl-substituted Citrate-based
material having 4 to 9 carbon atoms and a non-hybrid alkylsubstituted
Citrate-based material having 4 to 9 carbon atoms.
20 11. The plasticizer composition of claim 1, wherein the
Citrate-based material is a non-hybrid alkyl-substituted
Citrate-based material having 4 to 9 carbon atoms, and
an alkyl group having 4 to 9 carbon atoms of the
Citrate-based material is a linear chain or a branched chain.
25
62
12. The plasticizer composition of claim 1, further
comprising an epoxidized oil.
13. The plasticizer composition of claim 12, wherein the
epoxidized oil is included in an amount of 1 parts by 5 weight
to 100 parts by weight based on 100 parts by weight of the
plasticizer composition.
14. The plasticizer composition of claim 12, wherein the
10 epoxidized oil comprises at least one 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.
15
15. A method of preparing a plasticizer composition, the
method comprising:
preparing a terephthalate-based material and a Citratebased
material; and
20 obtaining a plasticizer compound by blending the
terephthalate-based material and the Citrate-based material
in a weight ratio of 99:1 to 1:99,
wherein the terephthalate-based material is a single
compound or a mixture.
25
63
16. The method of claim 15, wherein, when the
terephthalate-based material is the single compound, the
terephthalate compound is prepared by a direct esterification
reaction in which terephthalic acid reacts with at least one
alcohol selected from the group consisting of 2-5 ethylhexyl
alcohol, isononyl alcohol, butyl alcohol, and isobutyl
alcohol.
17. The method of claim 15, wherein, when the
10 terephthalate-based material is the mixture, the
terephthalate compound is prepared by:
a direct esterification reaction in which terephthalic
acid reacts with at least one alcohol selected from the group
consisting of 2-ethylhexyl alcohol, isononyl alcohol, butyl
15 alcohol, and isobutyl alcohol; or
a transesterification reaction in which any one
terephthalate selected from di(2-ethylhexyl)terephthalate or
diisononyl terephthalate reacts with any one alcohol selected
from butyl alcohol or isobutyl alcohol.
20
18. A resin composition comprising:
100 parts by weight of a resin; and
5 parts by weight to 150 parts by weight of the
plasticizer composition of claim 1.
25
64
19. The resin composition of claim 18, wherein the resin
comprises at least one selected from the group consisting of
ethylene vinyl acetate, polyethylene, polypropylene,
polyvinyl chloride, polystyrene, polyurethane, and a
thermoplastic elastomer5 .
20. The resin composition of claim 18, wherein the resin
composition is a material of at least one product selected
from the group consisting of electric wires, flooring
10 materials, automotive interior materials, films, sheets,
wallpaper, and tubes.