WO2016129876A1 - Plasticizer composition, resin composition, and preparation methods therefor - Google Patents

Abstract

The present invention relates to a plasticizer composition, a resin composition, and preparation methods therefor, and can provide: a plasticizer capable of improving physical properties such as plasticizing efficiency, migration, tensile strength, elongation, stress migration and light resistance, which are required in a sheet formulation, when used as a plasticizer of a resin composition, by improving inferior physical properties generated because of structural limitations; and a resin composition containing the same.

Description

Plasticizer composition, resin composition, and preparation method thereof

Citation with Related Applications

This application is filed with Korean Patent Application No. 10-2015-0021783 filed February 12, 2015, Korean Patent Application No. 10-2015-0041794 filed March 25, 2015, and Korean Patent Application No. 10-2015 filed August 12, 2015 -0113875 and Korean Patent Application No. 10-2015-0144889, filed October 16, 2015, claiming the benefit of, all contents disclosed in the literature of that Korean patent application are incorporated as part of this specification.

Technical Field

The present invention relates to a plasticizer composition, a resin composition and a method for producing the same.

Typically, plasticizers react with alcohols to polycarboxylic acids such as phthalic acid and adipic acid to form the corresponding esters. In addition, in consideration of domestic and international regulations on phthalate-based plasticizers that are harmful to humans, research on plasticizer compositions that can replace phthalate-based plasticizers such as terephthalate-based, adipate-based, and other polymer-based plastics is being continued.

On the other hand, in order to manufacture products of flooring, wallpaper, sheet industry, etc., appropriate plasticizers should be used in consideration of discoloration, migration, processability, and the like. Plasticizers, fillers, stabilizers, viscosity-reducing agents, dispersants, antifoaming agents, foaming agents, etc. may be blended with PVC resins according to the tensile strength, elongation, light resistance, transferability, gelling properties, or processability, which are required for various industries in these various fields of use.

For example, among the plasticizer compositions applicable to PVC, when dioctyl terephthalate, which is relatively inexpensive, is applied, the viscosity of the plasticizer is high, the absorption rate of the plasticizer is relatively low, and the performance is not good.

Accordingly, by developing a product superior to the dioctyl terephthalate or a product of a new composition including dioctyl terephthalate, research on a technology that can be optimally applied as a plasticizer for vinyl chloride resins is required.

Accordingly, the inventors have identified a plasticizer composition that can improve the poor physical properties caused by structural limitations while continuing to study the plasticizer, and have completed the present invention.

That is, an object of the present invention is to provide a plasticizer capable of improving the physical properties such as plasticization efficiency, transferability, gelling properties required in the prescription of the sheet, etc. when used as a plasticizer of the resin composition, a method for producing the same and a resin composition comprising the same have.

According to an embodiment of the present invention to solve the above problems, a terephthalate-based material; And a citrate-based compound, wherein the weight ratio of the terephthalate-based material to the citrate-based compound is 99: 1 to 1:99.

The weight ratio of the terephthalate-based material to citrate-based compound may be 95: 5 to 50:50.

The weight ratio of the terephthalate-based material to citrate-based compound may be 95: 5 to 60:40.

The terephthalate-based material is di (2-ethylhexyl) terephthalate (DEHTP or DOTP), diisononyl terephthalate (DINTP), dibutyl terephthalate (DBTP), butyl isononyl terephthalate (BINTP), butyl ( It may be a single compound selected from the group consisting of 2-ethylhexyl) terephthalate (BEHTP or BOTP) and (2-ethylhexyl) isononyl terephthalate (EHINTP or OINTP) or a mixture of one or more compounds.

The single compound may be di (2-ethylhexyl) terephthalate or diisononyl terephthalate.

The mixture is a first mixture of di (2-ethylhexyl) terephthalate, butyl (2-ethylhexyl) terephthalate and dibutyl terephthalate, or diisononyl terephthalate, butylisononyl terephthalate and dibutyl The terephthalate may be a mixed second mixture or a third mixture of di (2-ethylhexyl) terephthalate, (2-ethylhexyl) isononyl terephthalate and diisononyl terephthalate.

The first mixture is di- (2-ethylhexyl) terephthalate 3.0 to 99.0 mol%; 0.5 to 96.5 mol% butyl (2-ethylhexyl) terephthalate and 0.5 to 96.5 mol% dibutyl terephthalate;

The second mixture is diisononyl terephthalate 3.0 to 99.0 mol%; 0.5 to 96.5 mol% butyl isononyl terephthalate and 0.5 to 96.5 mol% dibutyl terephthalate;

The third mixture is di- (2-ethylhexyl) terephthalate 3.0 to 99.0 mol%; 0.5 to 96.5 mol% of (2-ethylhexyl) isononyl terephthalate and 0.5 to 96.5 mol% of diisononyl terephthalate;

The citrate compound may include any one selected from the group consisting of a hybrid alkyl substituted citrate compound having 4 to 9 carbon atoms and a non-hybrid alkyl substituted citrate compound having 4 to 9 carbon atoms.

The citrate compound may be a non-hybrid alkyl substituted citrate compound having 4 to 9 carbon atoms, and the alkyl group having 4 to 9 carbon atoms of the citrate compound may be linear or branched.

The plasticizer composition may further comprise an epoxidized oil.

The epoxidized oil may include 1 to 100 parts by weight based on 100 parts by weight of the plasticizer composition.

The epoxidized oil is epoxidized soybean oil, epoxidized castor oil, epoxidized linseed oil, epoxidized palm oil, epoxidized stearic acid acid), epoxidized oleic acid, epoxidized tall oil, and epoxidized linoleic acid.

According to an embodiment of the present invention to solve the above problems, preparing a terephthalate-based material and a citrate-based compound; And blending the terephthalate-based material and the citrate-based compound in a weight ratio of 99: 1 to 1:99 to obtain a plasticizer composition, wherein the terephthalate-based material is a single compound or a mixture. Provided is a method for preparing.

When the terephthalate-based material is a mixture, a direct esterification reaction of one or more alcohols selected from the group consisting of 2-ethylhexyl alcohol, isononyl alcohol, butyl alcohol and isobutyl alcohol and terephthalic acid; Or a trans esterification reaction of any one of terephthalate selected from di (2-ethylhexyl) terephthalate or diisononyl terephthalate and an alcohol selected from butyl alcohol or isobutyl alcohol; and a terephthalate compound through Can be prepared.

According to an embodiment of the present invention to solve the above problems, 100 parts by weight of resin; And 5 to 150 parts by weight of the plasticizer composition of claim 1 is provided.

The resin may be at least one member selected from the group consisting of ethylene vinyl acetate, polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyurethane, and thermoplastic elastomers.

The resin composition may be at least one material selected from the group consisting of wires, flooring materials, automotive interior materials, films, sheets, wallpaper, and tubes.

When used in a resin composition, the plasticizer composition according to an embodiment of the present invention may provide excellent physical properties such as migration resistance and volatility, as well as excellent plasticization efficiency and tensile strength and elongation.

1 is an image taken the results of testing the heat resistance of the resin containing a plasticizer composition according to the present invention.

Figure 2 is an image of the result of testing the heat resistance of the resin containing a plasticizer composition according to the present invention.

Figure 3 is an image of the result of testing the thermal stability of the resin containing a plasticizer composition according to the present invention.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

First, the present invention has a technical feature to provide a plasticizer composition that can improve the poor physical properties caused by the structural limitations.

According to an embodiment of the present invention can provide a plasticizer composition containing a terephthalate-based material. Specifically, the terephthalate-based material has a content selected from the range of 1 to 99% by weight, 20 to 99% by weight, 40 to 99% by weight, 50 to 95% by weight or 60 to 90% by weight, based on the total weight of the composition. Can be applied.

The terephthalate-based material may be one having, for example, an end group independently selected from alkyl groups having 1 to 12 carbon atoms, 3 to 11 carbon atoms, 4 to 10 carbon atoms, 8 to 10 carbon atoms, 8 to 9 carbon atoms, or 8 carbon atoms.

The terephthalate-based material is di (2-ethylhexyl) terephthalate (DEHTP or DOTP), diisononyl terephthalate (DINTP), dibutyl terephthalate (DBTP), butyl isononyl terephthalate (BINTP), butyl ( It may be a single compound selected from the group consisting of 2-ethylhexyl) terephthalate (BEHTP or BOTP) and (2-ethylhexyl) isononyl terephthalate (EHINTP or OINTP), and may be a mixture of one or more compounds.

More specifically, when the terephthalate-based material is a single compound, it may be di (2-ethylhexyl) terephthalate or diisononyl terephthalate, and when the terephthalate-based material is a mixture of three terephthalate-based The substance may be mixed, for example, a first mixture of di (2-ethylhexyl) terephthalate, butyl (2-ethylhexyl) terephthalate and dibutylterephthalate, diisononyl terephthalate, butyl The second mixture of isononyl terephthalate and dibutyl terephthalate, the third mixture of di (2-ethylhexyl) terephthalate, (2-ethylhexyl) isononyl terephthalate and diisononyl terephthalate Can be.

Specifically, in the case of the first to the third mixture, it may have a specific composition ratio, the first mixture is di (2-ethylhexyl) terephthalate 3.0 to 99.0 mol%; Butyl (2-ethylhexyl) terephthalate 0.5 to 96.5 mol% and dibutyl terephthalate 0.5 to 96.5 mol%; wherein the second mixture is diisononyl terephthalate 3.0 to 99.0 mol%; Butyl isononyl terephthalate 0.5 to 96.5 mol% and dibutyl terephthalate 0.5 to 96.5 mol%; wherein the third mixture is di (2-ethylhexyl) terephthalate 3.0 to 99.0 mol%; 0.5 to 96.5 mol% of (2-ethylhexyl) isononyl terephthalate and 0.5 to 96.5 mol% of diisononyl terephthalate;

The composition ratio may be a mixture composition ratio produced by the esterification reaction, and may be an intended composition ratio by additionally mixing a specific compound, and the mixture composition ratio may be appropriately adjusted to suit desired physical properties.

In addition, according to an embodiment of the present invention, the plasticizer composition may further include a citrate-based compound, the citrate-based compound is a C4 to 9 hybrid alkyl substituted citrate-based compound and a ratio of 4 to 9 carbon atoms It may include one or more compounds selected from the group consisting of mixed alkyl substituted citrate compounds.

The alkyl alkyl substituted citrate compound having 4 to 9 carbon atoms is, for example, 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-butyl 2,3-bis (2-ethylhexyl) 2-hydroxypropane 4 and 8 carbon atoms such as -1,2,3-tricarboxylate or 2-butyl 1,3-bis (2-ethylhexyl) 2-hydroxypropane-1,2,3-tricarboxylate Citrate having a combination substituent of an alkyl group; 1,2-dipentyl 3-heptyl 2-hydroxypropane-1,2,3-tricarboxylate, 1,3-dipentyl 2-heptyl 2-hydroxypropane-1,2,3-tricarboxyl Rate, 1-pentyl 2,3-diheptyl 2-hydroxypropane-1,2,3-tricarboxylate, or 2-butyl 1,3-diheptyl 2-hydroxypropane-1,2,3- Citrate having a combination substituent of an alkyl group having 5 and 7 carbon atoms, such as tricarboxylate, and the like. In addition to this, a citrate having a combination substituent of two alkyl groups having 4 to 9 carbon atoms and having different carbon atoms may be selected. This may be applied, the alkyl group may be straight or branched chain.

In the non-hybrid alkyl substituted citrate compound having 4 to 9 carbon atoms, the alkyl group having 4 to 9 carbon atoms may be linear or branched. For example, tributyl citrate (TBC) and tripentyl citrate (TPC). , Trihexyl citrate (THC), triheptyl citrate (THC), trioctyl citrate (TOC), trinonyl citrate (TNC) and the like can be applied, and the butyl to nonyl groups are the respective structural isomers, such as In the case of a butyl group, an isobutyl group and a 2-ethylhexyl group may be included in an octyl group.

Although not limited thereto, non-hybrid alkyl substituted citrate compounds having 4 to 9 carbon atoms may be preferred, compared to hybrid alkyl substituted citrate compounds, and tributyl citrate and / or tri (2-ethylhexyl) sheets. The rate may be used at a slightly more frequent frequency.

Meanwhile, trialkyl citrate or dinalkyl-malkyl citrate may be applied, such as the hybrid or non-hybrid alkyl substituted citrate compound. When the acetyl group is present in the citrate compound, physical properties of the plasticizer, in particular, There exists a possibility that workability and gelling property may deteriorate with the fall of plasticization efficiency.

In other words, when the citrate compound is an acetyl citrate compound in which an acetyl group is substituted for hydrogen of the remaining hydroxy group in addition to the three ester groups, the plasticization efficiency is lowered, the amount of plasticizer to be overcome is increased, and the product price is increased. Due to such problems, deterioration in various aspects such as marketability, economic feasibility and physical properties may be a problem.

Here, the terephthalate-based material and the citrate-based compound in the plasticizer composition may be included in a weight ratio of 99: 1 to 1:99, 99: 1 to 20:80, 99: 1 to 40:60, 99: 1 to 50:50, or 99: 1 to 60:40, preferably 95: 5 to 50:50, or 90:10 to 60:40.

The plasticizer composition may include a terephthalate-based material and a citrate-based compound, and may further include an epoxidized oil. The epoxidized oil may include 1 to 100 parts by weight, preferably 1 to 80 parts by weight, based on 100 parts by weight of the plasticizer composition.

In the case of the mixed plasticizer composition of the terephthalate-based material and the citrate-based compound, among the various physical properties, the heat resistance may not be excellent, and the heat resistance may be compensated by further including the epoxidized oil, and epoxy If the content of the oxidized oil exceeds 100 parts by weight, there is a concern that the physical properties such as the aging resistance, volatility, and tensile strength of the mixed plasticizer composition may be relatively lowered, and when it contains less than 1 part by weight, the heat resistance characteristics are compensated for. The problem may arise. However, if possible, including 1 to 80 parts by weight may induce optimization of physical properties between heat resistance properties and tensile strength, migration resistance, etc., if not exceeding 100 parts by weight can be provided with a plasticizer composition of excellent physical properties .

The epoxidized oil is, for example, epoxidized soybean oil, epoxidized castor oil, epoxidized linseed oil, epoxidized palm oil, epoxidized palm oil, epoxidized stearic acid (epoxidized stearic acid), epoxidized oleic acid, epoxidized tall oil, epoxidized linoleic acid, or mixtures thereof. Preferably, epoxidized soybean oil (ESO), or epoxidized linseed oil (ELO) may be applied, but is not limited thereto.

Method for producing the plasticizer composition in the present invention, a blending method can be applied, the blending production method is as follows.

The plasticizer composition may be prepared by preparing a terephthalate-based material and a citrate-based compound and blending the terephthalate-based material and the citrate-based compound in a ratio of 1:99 to 99: 1 by weight. The phthalate-based material is characterized in that it is a single compound or mixture.

When the terephthalate-based material is a single compound, terephthalate through direct esterification reaction of at least one alcohol selected from the group consisting of 2-ethylhexyl alcohol, isononyl alcohol, butyl alcohol and isobutyl alcohol and terephthalic acid; Compounds can be prepared.

The direct esterification may include adding terephthalic acid to an alcohol, then adding a catalyst and reacting under a nitrogen atmosphere; Removing unreacted alcohol and neutralizing unreacted acid; And dehydration and filtration by distillation under reduced pressure.

In addition, the alcohol used in the blending production method is in the range of 150 to 500 mol%, 200 to 400 mol%, 200 to 350 mol%, 250 to 400 mol%, or 270 to 330 mol% based on 100 mol% of terephthalic acid. Can be used.

Further, the alcohol used in the blending production method is in the range of 150 to 500 mol%, 200 to 400 mol%, 200 to 350 mol%, 250 to 400 mol%, or 270 to 330 mol% based on 100 mol% of terephthalic acid. Can be used.

On the other hand, the catalyst used in the blending production method is, for example, sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid, paratoluenesulfonic acid, methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, alkyl sulfuric acid and other acid catalysts, aluminum lactate, lithium fluoride Metal salts such as potassium chloride, cesium chloride, calcium chloride, iron chloride, aluminum phosphate, metal oxides such as heteropolyacids, natural / synthetic zeolites, cation and anion exchange resins, tetraalkyl titanate and organic metals such as polymers thereof. It may be one or more selected. As a specific example, the catalyst may use tetraalkyl titanate.

The amount of the catalyst used may vary depending on the type, for example, in the case of a homogeneous catalyst, 0.01 to 5% by weight, 0.01 to 3% by weight, 1 to 5% by weight or 2 to 4% by weight based on 100% by weight of the total reactants. And, in the case of heterogeneous catalysts, it may be in the range of 5 to 200%, 5 to 100%, 20 to 200%, or 20 to 150% by weight of the total amount of reactants.

In this case, the reaction temperature may be in the range of 180 to 280 ° C, 200 to 250 ° C, or 210 to 230 ° C.

When the terephthalate-based material is a mixture, the terephthalate compound may be prepared and mixed through the aforementioned direct esterification reaction, or any one selected from di (2-ethylhexyl) terephthalate or diisononyl terephthalate A terephthalate compound may be prepared through a trans esterification reaction in which one terephthalate compound and one alcohol selected from butyl alcohol or isobutyl alcohol are reacted.

As used herein, the "trans-esterification reaction" refers to a reaction in which an alcohol reacts with an ester as shown in Scheme 1, where R " of the ester is interchanged with R ′ of the alcohol as shown in Scheme 1 below:

Scheme 1

According to an embodiment of the present invention, when the trans-esterification reaction occurs when the alkoxide of the alcohol attacks the carbon of two ester (RCOOR '') groups present in the ester compound; When attacking carbon of two ester (RCOOR ")groups; In the three cases, three kinds of ester compositions may be generated by water.

In addition, the trans-esterification reaction has the advantage that does not cause a waste water problem compared to the acid-alcohol esterification reaction, and can proceed under a non-catalyst, it can solve the problem when using an acid catalyst.

For example, di (2-ethylhexyl) terephthalate and butyl alcohol may be prepared by di- (2-ethylhexyl) terephthalate, butyl (2-ethylhexyl) terephthalate and dibutylterephthalate by the trans-esterification reaction. Can be produced, wherein the three terephthalates are formed in amounts of 3.0% to 70%, 0.5% to 50%, and 0.5% to 85% by weight relative to the total weight of the mixture, respectively. And may be specifically formed in amounts of 10% to 50%, 0.5% to 50%, and 35% to 80% by weight. Within this range, there is an effect of obtaining a terephthalate-based material (mixture) having high process efficiency and excellent processability and absorption rate.

In addition, the mixture prepared by the trans-esterification reaction can control the composition ratio of the mixture according to the amount of alcohol added.

The amount of the alcohol added may be 0.1 to 89.9 parts by weight, specifically 3 to 50 parts by weight, and more specifically 5 to 40 parts by weight based on 100 parts by weight of the terephthalate compound.

Since the molar fraction of the terephthalate compound participating in the trans-esterification reaction will increase as the terephthalate compound contains more alcohol, the content of the two terephthalate compounds as a product in the mixture may increase. And, correspondingly, the content of the unreacted terephthalate compound may show a tendency to decrease.

According to one embodiment of the present invention, the molar ratio of the reactant terephthalate compound and the alcohol is, for example, 1: 0.005 to 5.0, 1: 0.05 to 2.5, or 1: 0.1 to 1.0, within this range, high process efficiency and processability There is an effect of obtaining an ester plasticizer composition excellent in an improvement effect.

However, the composition ratio of the mixture of the three terephthalate-based materials is not limited to the above range, and the composition ratio may be changed by additionally adding one of the three terephthalates, and the possible mixed composition ratio may be As shown.

According to one embodiment of the invention, the trans-esterification reaction is carried out for 10 minutes to 10 hours, preferably at a reaction temperature of 120 to 190 ℃, preferably 135 to 180 ℃, more preferably 141 to 179 ℃ It is preferably carried out at 30 minutes to 8 hours, more preferably 1 to 6 hours. It is possible to effectively obtain a mixture that is a terephthalate-based material of a desired composition ratio within the temperature and time range. In this case, the reaction time may be calculated from the time point at which the reaction temperature is reached after the reaction temperature is raised.

The trans-esterification reaction may be carried out under an acid catalyst or a metal catalyst, in which case the reaction time is shortened.

The acid catalyst may be, for example, sulfuric acid, methanesulfonic acid or p-toluenesulfonic acid, and the like, and the metal catalyst may be, for example, an organometallic catalyst, a metal oxide catalyst, a metal salt catalyst, or the metal itself.

The metal component may be any one selected from the group consisting of tin, titanium and zirconium, or a mixture of two or more thereof.

In addition, after the trans-esterification reaction may further comprise the step of distilling off the unreacted alcohol and reaction by-products, for example, the ester compound represented by the formula (3).

The distillation may be, for example, two-stage distillation that is separated by using a difference between the break points of the alcohol and the reaction by-product.

In another example, the distillation may be mixed distillation. In this case, there is an effect that the ester plasticizer composition can be relatively stable at a desired composition ratio. The mixed distillation means distilling butanol and reaction by-products simultaneously.

The direct esterification and trans esterification reactions can also be used to prepare the above-mentioned hybrid or non-hybrid citrate compounds. In this case, like the terephthalate-based material, the citrate-based compound may also be prepared in a mixed ratio in a predetermined ratio, and may control the composition ratio of the mixture to be produced by adjusting the content of alcohol as a reaction raw material. In addition, when the citrate compound is prepared through a direct esterification reaction or a trans esterification reaction, the contents thereof may be applied in the same manner as the contents applied to preparing the terephthalate-based material.

The plasticizer composition thus prepared is 5 to 150 parts by weight, 40 to 100 parts by weight, or 100 parts by weight of a resin selected from ethylene vinyl acetate, polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyurethane, and thermoplastic elastomer. It can be included within the range of 40 to 50 parts by weight to provide a resin composition that is effective for all compound formulations, sheet formulations and plastisol formulations.

In one example, the plasticizer composition can be applied to the production of wires, flooring, automotive interior, film, sheet, wallpaper or tube.

Example

Hereinafter, the present invention will be described in detail with reference to Examples. However, embodiments according to the present invention can be modified in many different forms, the scope of the present invention should not be construed as limited to the embodiments described below. The embodiments of the present invention are provided to more completely explain the present invention to those skilled in the art.

Preparation Example 1 Preparation of DOTP

498.0 g of purified terephthalic acid (TPA), 1170 g of 2-ethylhexyl alcohol (2-EH) in a four-necked three-liter reactor equipped with a chiller, condenser, decanter, reflux pump, temperature controller, and stirrer -EH molar ratio (1.0): (3.0)), 1.54 g (0.31 parts by weight based on 100 parts by weight of TPA) of a titanium catalyst (TIPT, tetra isopropyl titanate) was added as a catalyst, and the temperature was gradually raised to about 170 ° C. . The production of water was started at about 170 ° C., and the reaction was carried out for about 4.5 hours while nitrogen gas was continuously added at a reaction temperature of about 220 ° C. and atmospheric pressure. The reaction was terminated when the acid value reached 0.01.

After the reaction is completed, distillation is performed under reduced pressure for 0.5 to 4 hours to remove unreacted raw materials. In order to remove unreacted raw materials below a certain content level, steam extraction is performed under reduced pressure using steam for 0.5 to 3 hours, the reaction solution temperature is cooled to about 90 ° C., and neutralization is performed using an alkaline solution. . In addition, washing with water may be performed, and then the reaction solution is dehydrated to remove moisture. The filtrate was added to the reaction solution from which the water was removed, the resultant was stirred for a while, and then filtered to obtain 1326.7 g (yield: 99.0%) of di-2-ethylhexyl terephthalate.

Preparation Example 2 Preparation of DINTP

DINTP was prepared in the same manner as in Preparation Example 1, except for using isononyl alcohol instead of 2-ethylhexyl alcohol in the esterification reaction.

Preparation Example 3 Preparation of DOTP / BOTP / DBTP Mixture (First Mixture) (GL500)

2000 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 DOTP) were added to a reactor equipped with a stirrer, a condenser, and a decanter, followed by 2 at a reaction temperature of 160 under a nitrogen atmosphere. Trans-esterification reaction for a period of time to dibutylterephthalate (DBTP), butylisononylterephthalate (BINTP) and diisononyl terephthalate (DINTP) in the range of 4.0%, 35.0% and 61.0% by weight, respectively. An ester plasticizer composition was obtained.

The reaction product was mixed and distilled to remove butanol and 2-ethylhexyl alcohol and finally to prepare a first mixture.

Preparation Example 4 Preparation of DINTP / OINTP / DOTP Mixture (Third Mixture) (GL100)

498.0 g of purified terephthalic acid (TPA), 975 g of 2-ethylhexyl alcohol (2-EH) in a four-necked three-liter reactor equipped with a chiller, condenser, decanter, reflux pump, temperature controller, and stirrer. -Molar ratio of EH (1.0) :( 2.5)) and 216.5 g of isononyl alcohol (INA) (molar ratio of TPA: INA (1.0) :( 0.5)) were added, and a titanium-based catalyst (TIPT, tetra isopropyl) was used as a catalyst. titanate) was charged with 1.54 g (0.31 parts by weight based on 100 parts by weight of TPA), and the temperature was slowly raised to about 170 ° C. The production of water was started at about 170 ° C., and the reaction was carried out for about 4.5 hours while nitrogen gas was continuously added at a reaction temperature of about 220 ° C. and atmospheric pressure. The reaction was terminated when the acid value reached 0.01.

After the reaction is completed, distillation is performed under reduced pressure for 0.5 to 4 hours to remove unreacted raw materials. In order to remove unreacted raw materials below a certain content level, steam extraction is performed under reduced pressure using steam for 0.5 to 3 hours, the reaction solution temperature is cooled to about 90 ° C., and neutralization is performed using an alkaline solution. . In addition, washing with water may be performed, and then the reaction solution is dehydrated to remove moisture. The filtrate was added to the reaction solution from which the water had been removed, stirred for a predetermined time, and filtered to obtain a third mixture.

Preparation Example 5 Preparation of TBC

384 g of citric acid and 580 g of butanol were used as reaction raw materials, and finally, 706 g (yield: 98%) of tributyl citrate were obtained.

Preparation Example 6 Preparation of TOC

Finally, 1029 g (yield: 98%) of tri-2-ethylhexyl citrate was obtained using 384 g of citric acid and 1014 g of 2-ethylhexanol as reaction materials.

Preparation Example 7 Preparation of TPC

384 g of citric acid and 688 g of 1-pentanol were used as reaction raw materials to finally obtain 796 g (yield: 98%) of tripentyl citrate.

Preparation Example 8 Preparation of THC

Finally, 384 g of citric acid and 797 g of n-hexanol were used as reaction materials to finally obtain 878 g (yield: 98%) of trihexyl citrate.

Preparation Example 9 Preparation of TiBC

384 g of citric acid and 580 g of isobutanol were used as reaction raw materials, and finally 706 g (yield: 98%) of triisobutyl citrate was obtained.

Preparation Example 10 Preparation of TiNC

384 g of citric acid and 1123 g of isononanol were used as reaction raw materials to finally obtain 1111 g (yield: 98%) of triisobutyl citrate.

Preparation Example 11 Preparation of BOC-A

As a reaction raw material, a trans esterification reaction was performed using 1000 g of TOC prepared in Preparation Example 6 and 300 g of n-butanol, and finally 840 g of butyloctyl citrate was obtained. For reference, the product is a composition, the main components are divided into alkyl groups bonded to the three ester groups of the citrate compound, BOC two butyl groups, BOC one butyl group and TOC unbutylated, respectively The ratio of was about 20%, 50% and 30% by weight.

Preparation Example 12 Preparation of BOC-B

The trans esterification reaction was carried out using 1000 g of TOC prepared in Preparation Example 6 and 150 g of n-butanol as reaction raw materials, and finally 940 g of butyloctyl citrate was obtained. For reference, the product is a composition, the main components are divided into alkyl groups bonded to the three ester groups of the citrate compound, BOC two butyl groups, BOC one butyl group and TOC unbutylated, respectively The ratio of was about 10%, 40% and 50% by weight.

The plasticizer composition of Examples 1 to 17 was prepared by mixing the materials prepared in Preparation Examples 1 to 12, and the plasticizer compositions of Examples 1 to 17 were summarized in Tables 1 to 5, and the physical properties of the plasticizer composition were evaluated in the following test items. Followed.

	Terephthalate	Citrate Compound	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
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
Example 8-3			6: 4

	Terephthalate	Citrate Compound	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

	Terephthalate	Citrate Compound	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

	Terephthalate	Citrate Compound	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

	Terephthalate	Citrate Compound	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

<Test item>

Hardness Measurement

Using ASTM D2240, shore hardness at 25 ° C., 3T 10s was measured.

Tensile strength measurement

By the ASTM D638 method, the cross head speed was pulled to 200 mm / min (1T) using a test instrument, UTM (manufacturer; Instron, model name; 4466), and the point where the specimen was cut was measured. . Tensile strength was calculated as follows:

Tensile Strength (kgf / mm2) = Load Value (kgf) / Thickness (mm) x Width (mm)

Elongation Rate Measurement

By using the ASTM D638 method, the crosshead speed was pulled to 200 mm / min (1T) using the U.T.M, and then measured at the point where the specimen was cut, the elongation was calculated as follows:

Elongation (%) = [length after extension / initial length] x 100.

Migration loss measurement

Specimens with a thickness of 2 mm or more were obtained according to KSM-3156. A PS plate was attached to both sides of the specimen and a load of 1 kgf / cm ² was applied. The specimen was left in a hot air circulation oven (80 ° C.) for 72 hours and then taken out and cooled at room temperature for 4 hours. Then, after removing the PS attached to both sides of the test piece, the weight before and after leaving in the oven was measured and the transfer loss was calculated by the following equation.

% Of transfer loss = [(initial weight of specimen at room temperature-weight of specimen after leaving the oven) / initial weight of specimen at room temperature] x 100

Measurement of volatile loss

After working the prepared specimen at 80 ℃ for 72 hours, the weight of the specimen was measured.

Heat loss (%) = [(initial specimen weight-specimen weight after operation) / initial specimen weight] x 100.

Stress testing

In the stress test, the specimen was bent at room temperature for a period of time, and then observed the degree of transition (soaking), the degree was expressed as a numerical value, the closer to 0, the better the characteristics.

Light resistance measurement

By the method of ASTM 4329-13, the specimen was placed in a QUV and irradiated with UV for 200 hours, and then the change in color was calculated using a reflectometer.

Heat resistance measurement

The discoloration degree of the initial specimen by the heating loss measurement method and the specimen after the heating loss test were measured. The measured value was determined by changing the value of E against L, a, b using the colormeter.

Experimental Example 1: DOTP plasticizer composition

1. Mixed plasticizer composition of DOTP and TBC

DOTP and TBC were mixed in the mixing ratios of Examples 1-1 to 1-5 described in Table 1 to obtain a mixed plasticizer composition, which was used as an experimental specimen.

For the specimen preparation, reference to ASTM D638, 40 parts by weight of mixed plasticizer composition, 2.5 parts by weight of auxiliary stabilizer (ESO), 3 parts by weight of stabilizer (LOX-430W) in 100 parts of PVC at 98 ℃ in 3L super mixer After mixing under 700 rpm under a roll mill, it worked for 4 minutes at 160 ° C to make a 5 mm sheet, press work for 2 minutes at high pressure for 2.5 minutes at low pressure at 180 ° C, and then made a sheet of 1 to 3 mm to prepare a specimen. . Each specimen was used to evaluate the physical properties according to the test items described above, and the results are summarized in Table 6 below.

	Plasticizer	Shore "A"	Tensile Strength (kg / cm 2 )	% Elongation	Performance loss (%)	Heating loss (%)	Light resistance (E)	Absorption rate (sec)	Stress test (24 hours)
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
Comparative Example 1	DOP	88.2	203.4	289.6	3.56	6.64	1.13	408	1.0
Comparative Example 2	DOTP	89.4	222.1	324.9	0.25	2.75	2.71	465	3.0

As shown in Table 6, when comparing Comparative Examples 1 to 2 and Examples 1-1 to 1-5 using DOP and DOTP plasticizers that are commercially widely sold, hardness, absorption rate, and tensile strength Strength, elongation and stress resistance It can be seen that the properties are better or equal in all physical properties, and further improve the thirteen physical properties of existing plasticizer products.

On the other hand, when the absorption rate of the plasticizer is fast, there is an advantage in that the processability is excellent, even if too short may cause problems due to the gelling during processing may need to be maintained an appropriate absorption rate. From this point of view, in the case of Examples 1-4 and 1-5 in which the TBC is excessively mixed, the absorption rate is rather fast, and when the plasticizer composition is used, gelling problems may occur during processing. In the case of Examples 1-1 to 1-3 in which the amount of was appropriately adjusted, it was confirmed that this problem did not occur due to absorption for an appropriate time. Furthermore, it can also be confirmed that the difference in physical properties is large even in the case of heating loss by adjusting the mixing ratio. Therefore, it can be seen that a better plasticizer composition can be obtained by appropriately adjusting the mixing ratio.

2. Mixed plasticizer composition of DOTP and TOC

The mixed plasticizer composition was obtained by mixing DOTP and TOC in the mixing ratios of Examples 2-1 to 2-5 described in Table 1, which was used as a test specimen, and the specimen preparation and physical property evaluation were described in [1. Mixed plasticizer composition of DOTP and TBC] and the results are shown in Table 7 below.

	Plasticizer	Shore "A"	Tensile Strength (kg / cm 2 )	% Elongation	Performance loss (%)	Heating loss (%)	Light resistance (E)	Absorption rate (sec)	Stress test (24 hours)
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
Comparative Example 1	DOP	88.4	205.8	282.3	3.77	6.80	1.13	420	1.0
Comparative Example 2	DOTP	89.4	226.0	320.0	0.23	2.05	2.71	445	3.0

As shown in Table 7, comparing Comparative Examples 1 and 2 and Examples 2-1 to 2-5 using DOP and DOTP plasticizers, which are commercially widely sold products, compared to conventional DOTP products It can be seen that in all physical properties is better or equal or better, and further improved the thirteen physical properties of the existing plasticizer products.

On the other hand, also in relation to the absorption rate, it can be seen that in the case of Examples 2-1 to 2-3 is absorbed for a suitable time, in the case of Examples 2-4 and 2-5 it is required to take a very long time absorption rate It can be seen that this may cause deterioration of workability and productivity, and in some cases it may be further confirmed that it is necessary to be careful when excessively mixing TOC.

3. Mixed Plasticizer Composition of DOTP and TPC

DOTP and TPC (tripentyl citrate or triamyl citrate) were mixed in the mixing ratios of Examples 3-1 to 3-3 described in Table 1 to obtain a mixed plasticizer composition, which was used as a test specimen, and the preparation of the specimen was made at the time of sheet prescription. Except that BZ153T was used as a stabilizer, the above [1. Mixed plasticizer composition of DOTP and TBC] and the same evaluation was carried out, the results are shown in Table 8.

	Plasticizer	Shore "A"	Tensile Strength (kg / cm 2 )	% Elongation	Performance loss (%)	Heating 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
Comparative Example 1	DOP	88.4	205.8	282.3	3.77	6.80	1.13	1.0
Comparative Example 2	DOTP	91.8	226.3	318.2	1.65	0.76	2.56	2.0

As shown in Table 8, when comparing the comparative examples 1 and 2 using the DOP and DOTP plasticizer, which is a commercially widely sold product, and Examples 3-1 to 3-3, compared to the conventional DOTP product It can be seen that in all physical properties is better or equal or better, and further improved the thirteen physical properties of the existing plasticizer products.

4. Mixed Plasticizer Composition of DOTP and THC

DOTP and THC (trihexyl citrate) were mixed in the mixing ratios of Examples 4-1 to 4-3 shown in Table 1 to obtain a mixed plasticizer composition, which was used as a test specimen, and the specimen was prepared as a stabilizer when formulating a sheet BZ153T. Except for using [1. Mixed plasticizer composition of DOTP and TBC] and the same evaluation was carried out, the results are shown in Table 9 below.

	Plasticizer	Shore "A"	Tensile Strength (kg / cm 2 )	% Elongation	Performance loss (%)	Heating 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 4-3	5: 5	89.9	210.6	311.5	0.62	0.73	1.23	0.5
Comparative Example 1	DOP	88.4	205.8	282.3	3.77	6.80	1.13	1.0
Comparative Example 2	DOTP	91.8	226.3	318.2	1.65	0.76	2.56	2.0

As shown in Table 9, when comparing the comparative examples 1 and 2 using the DOP and DOTP plasticizer, which is a commercially widely sold product, and Examples 4-1 to 4-3, compared to the conventional DOTP product It can be seen that in all physical properties is better or equal or better, and further improved the thirteen physical properties of the existing plasticizer products.

5. Mixed Plasticizer Composition of DOTP and TiBC

DOTP and TiBC (triisobutyl citrate) were mixed in the mixing ratios of Examples 5-1 to 5-4 described in Table 1 to obtain a mixed plasticizer composition, which was used as a test specimen, and the test piece fabrication and physical property evaluation were evaluated by heating loss. Except for evaluating the trial working temperature to 100 ° C, the above [1. Mixed plasticizer composition of DOTP and TBC] and the results are shown in Table 10 below.

	Plasticizer	Shore "A"	Tensile Strength (kg / cm 2 )	% Elongation	Performance loss (%)	Heating 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

As shown in Table 10, when comparing Comparative Example 2 and Examples 5-1 to 5-4 using a commercially widely sold DOTP plasticizer, in terms of physical properties compared to conventional DOTP products It can be seen that it is better or equivalent, and further improves the thirteen physical properties of existing plasticizer products.

On the other hand, in the case of Examples 5-3 and 5-4 in which the TiBC is included in excess relative to the case of Examples 5-1 and 5-2, it can be confirmed that the tensile strength and elongation are lowered, and the transfer loss or the heating loss is reduced. You can see that this is much lower. In other words, it can be further confirmed that in some cases, it is necessary to be careful when excessively mixing TiBC.

6. Mixed Plasticizer Composition of DOTP and TiNC

DOTP and TiNC (triisononyl citrate) were mixed in the mixing ratios of Examples 6-1 to 6-5 described in Table 1 to obtain a mixed plasticizer composition, which was used as an experimental specimen. Except for using [1. Mixed plasticizer composition of DOTP and TBC] and the same evaluation was carried out, the results are shown in Table 11 below.

	Plasticizer	Shore "A"	Tensile Strength (kg / cm 2 )	% Elongation	Performance loss (%)	Heating 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

As shown in Table 11, when comparing the comparative example 2 using the DOTP plasticizer which is a commercially widely sold product, and Examples 6-1 to 6-4, in all physical properties compared to the conventional DOTP product It can be seen that it is better or equivalent, and further improves the thirteen physical properties of existing plasticizer products.

On the other hand, compared to the case of Examples 6-1 and 6-2 Examples 6-3 and 6-4 in which the excessive amount of TiNC is included, it can be seen that the plasticization efficiency is lowered as the hardness is greatly increased. That is, it was further confirmed that in some cases, it is necessary to be careful when excessively mixing TiNC.

7. Mixed plasticizer composition of DOTP and BOC

DOTP and BOC (butyloctyl citrate) are mixed and mixed in the mixing ratio of Examples 7-1 to 7-3 (BOC-A) and Examples 8-1 to 8-3 (BOC-B) described in Table 1 above. A plasticizer composition was obtained, which was used as a test specimen, except that BZ153T was used as a stabilizer when preparing a sheet. Mixed plasticizer composition of DOTP and TBC] and the same evaluation was carried out, the results are shown in Table 12 below.

	Plasticizer	Shore "A"	Tensile Strength (kg / cm 2 )	% Elongation	Performance loss (%)	Heating loss (%)
Example 7-1	85:15	88.3	228.0	334.7	0.22	0.85
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

As shown in Table 12, when comparing Comparative Example 2, Examples 7-1 to 7-3 and Examples 8-1 to 8-3 using DOTP plasticizer which is a commercially widely sold product, It can be confirmed that it is superior or equivalent to the existing DOTP products, and in particular, the elongation characteristics and heating loss characteristics are improved.

Experimental Example 2: DINTP plasticizer composition

1. Mixed plasticizer composition of DINTP and TBC

In the mixing ratio of Examples 9-1 to 9-4 described in Table 2, DINTP and TBC (tributyl citrate) were mixed to obtain a mixed plasticizer composition, and used as experimental specimens. Except for using [1. Mixed plasticizer composition of DOTP and TBC] and the same evaluation was carried out, the results are shown in Table 13.

	Plasticizer	Shore "A"	Tensile Strength (kg / cm 2 )	% Elongation	Performance loss (%)	Heating loss (%)	Light resistance (E)	Stress test (24 hours)
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
Comparative Example 4	DINTP	92.7	230.2	314.4	2.72	0.89	3.56	2.5
Comparative Example 5	TBC	86.3	202.4	301.4	6.99	15.38	1.33	0

As shown in Table 13, compared with Comparative Example 4 using a commercially widely available product DINTP plasticizer and Comparative Example 5, which does not contain a terephthalate-based material, and Examples 9-1 to 9-4 As a result, it can be seen that all physical properties are superior or equivalent to those of the conventional DINTP products, and further, the thirteen physical properties of the conventional plasticizer products are improved.

On the other hand, Examples 9-1 and 9-2 compared to the case of Examples 9-3 and 9-4 in which the excessive amount of TBC is included in the relative improvement in tensile strength and elongation characteristics can be confirmed that the effect is insignificant. . That is, it was further confirmed that in some cases, it is necessary to be careful when excessively mixing the TBC.

2. Mixed plasticizer composition of DINTP and TOC

The mixed plasticizer composition was obtained by mixing DINTP and TOC (trioctyl citrate) in the mixing ratios of Examples 10-1 to 10-4 described in Table 2, which was used as experimental specimens. Except for using [1. Mixed plasticizer composition of DOTP and TBC], except that the evaluation was performed at a working temperature of 100 deg. Mixed plasticizer composition of DOTP and TBC], and the results are shown in Table 14 below.

	Plasticizer	Shore "A"	Tensile Strength (kg / cm 2 )	% Elongation	Performance loss (%)	Heating loss (%)	Light resistance (E)	Stress test (24 hours)
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
Comparative Example 4	DINTP	92.3	217.0	341.3	2.82	1.36	3.56	2.0
Comparative Example 6	TOC	91.3	230.1	369.0	0.82	0.82	1.35	0.5

As shown in Table 14, compared to Comparative Example 4 using a commercially widely available product DINTP plasticizer and Comparative Example 6, which does not contain a terephthalate-based material, and Examples 10-1 to 10-4 As a result, it can be seen that all physical properties are superior or equivalent to those of the conventional DINTP products, and further, the thirteen physical properties of the conventional plasticizer products are improved.

3. Mixed plasticizer composition of DINTP and TiBC

In the mixing ratio of Examples 11-1 to 11-4 described in Table 2, DINTP and TiBC (triisobutyl citrate) were mixed to obtain a mixed plasticizer composition, which was used as a test specimen. Except for using [1. Mixed plasticizer composition of DOTP and TBC], except that the evaluation was performed at a working temperature of 100 deg. Mixed plasticizer composition of DOTP and TBC], and the results are shown in Table 15 below.

	Plasticizer	Shore "A"	Tensile Strength (kg / cm 2 )	% Elongation	Performance loss (%)	Heating 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

As shown in Table 15, compared with Comparative Example 7 using a commercially widely commercially available product DINTP plasticizer and Comparative Example 7, which does not include a terephthalate-based material, Examples 11-1 to 11-4 As a result, it can be seen that all physical properties are superior or equivalent to those of the conventional DINTP products, and further, the thirteen physical properties of the conventional plasticizer products are improved.

On the other hand, compared with Examples 11-1 and 11-2, Examples 11-3 and 11-4 in which excess TiBC is included can be confirmed that the improvement effect in the tensile strength and elongation characteristics are insignificant. . That is, it was further confirmed that in some cases, it is necessary to be careful when excessively mixing TiBC.

Experimental Example 3: Mixed plasticizer composition of the first mixture and BOC

The first mixture of Preparation Example 3 (DOTP / BOTP) in a mixing ratio of Examples 12-1 to 12-3 (BOC-A) and Examples 13-1 to 13-3 (BOC-B) described in Table 3 above. / DBTP) and BOC (butyloctyl citrate) were mixed to obtain a mixed plasticizer composition, which was used as a test specimen. Except that BZ153T was used as a stabilizer, as described in [1. Mixed plasticizer composition of DOTP and TBC] and the same evaluation was carried out, the results are shown in Table 16 and 17.

	Plasticizer	Shore "A"	Tensile Strength (kg / cm 2 )	% Elongation	Performance loss (%)	Heating 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

Stress test	24 hours	72 hours	168 hours elapsed
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

As shown in Table 16 and 17, Comparative Example 8, Example 12-1 to 12-3 and Examples 13-1 to 13-3 using the mixed plasticizer composition which is a mixed composition of DOTP, BOTP and DBTP By doing so, it can be confirmed that it is superior or equivalent to the existing products.

Experimental Example 4: Mixed plasticizer composition of the third mixture and TBC or TOC

Example 14-1 to 14-4 described in Table 4, and the third mixture (DINTP / OINTP / DOTP) of Preparation Example 4, tributyl citrate (TBC) or trioctyl (TBC) in the mixing ratio of Example 15-1 citrate) was mixed to obtain a mixed plasticizer composition, which was used as a test specimen, and the specimen preparation and physical property evaluation were performed in the same manner, and the results are shown in Tables 18 and 19.

	Plasticizer	Shore "A"	Tensile Strength (kg / cm 2 )	% Elongation	Performance loss (%)	Heating 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	Tertiary mixture	92.8	254.4	309.0	2.03	0.72	5.23

Stress test	24 hours	72 hours	168 hours elapsed
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

As shown in Tables 18 and 19, comparing Comparative Example 9, Examples 14-1 to 14-4 and Example 15-1 using a mixed plasticizer composition which is a mixed composition of DINTP, OINTP and DOTP, It can be confirmed that it is better or equivalent than the product of.

On the other hand, compared to the case of Examples 14-1 to 14-3, in the case of Example 14-4 containing a relatively excessive amount of TBC, it can be confirmed that the tensile strength and elongation characteristics are lowered, and the heating loss is also inferior. . That is, it was further confirmed that in some cases, it is necessary to be careful when excessively mixing the TBC.

Experimental Example 5: Mixed plasticizer composition of DOTP and TBC and epoxidized oil

1. Mixed plasticizer composition of DOTP, TBC and ESO

DOTP, TBC, and ESO were mixed at the mixing ratios of Examples 16-1 to 16-5 described in Table 5 to obtain a mixed plasticizer composition, which was used as an experimental specimen. Except for the addition of parts by weight, no addition of auxiliary stabilizer (ESO), and addition of 0.5 parts by weight of titanium dioxide (TiO ₂ ), the above [1. Mixed plasticizer composition of DOTP and TBC], and the same evaluation was carried out, the results are shown in Table 20, and the heat resistance test results are shown in Figures 1 and 2.

	Plasticizer	Shore "A"	Tensile Strength (kg / cm 2 )	% Elongation	Performance loss (%)	Heating 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

As shown in Table 20, when comparing Examples 16-1 to 16-5 and Comparative Example 2 which is a DOTP plasticizer composition as a conventionally used product, the plasticizer composition of the examples is better than the existing product or It can confirm that it is equivalent or more.

On the other hand, as a result of the heat resistance test, referring to the image of Figures 1 and 2, in the case of Example 1-2 without the addition of the epoxidized oil it can be confirmed that it is vulnerable to black tanned due to heat, but a predetermined amount of epoxidized oil is added In this case, it can be seen that there is no change. In other words, when the citrate-based compound is added to improve the physical properties of the existing product DOTP, the heat resistance may be somewhat weak, but at the same time, when the epoxidized oil is added, the heat resistance may be maintained and improved. .

In addition, as shown in the above data, not only the ratio of the plasticizer composition and the epoxidized oil is 9: 1 to 8: 2 to complement the heat resistance property, but also the epoxidized oil up to the ratio of 6: 4 or 5: 5. Even if it is added to the plasticizer composition, a plasticizer composition can be prepared that can be compensated for the heat resistance characteristics while maintaining physical properties such as transfer loss, tensile strength, elongation.

2. Mixed plasticizer composition of DOTP, TOC and ESO

DOTP, TOC and ESO were mixed in the mixing ratios of Examples 17-1 to 17-3 described in Table 5 to obtain a mixed plasticizer composition, which was used as an experimental specimen.

The specimen is prepared by referring to ASTM D638, 50 parts by weight of mixed plasticizer composition, 40 parts by weight of filler (OMYA1T), 5 parts by weight of stabilizer (RUP-144), 0.3 parts by weight of lubricant (St-A), based on 100 parts by weight of PVC. After mixing at 700 rpm at 98 ° C. in a super mixer, a roll mill is used to work at 160 ° C. for 4 minutes to form a 5 mm sheet, press work at low pressure at 180 ° C. for 2.5 minutes and at high pressure for 2 minutes, 1 ~ A 3 mm sheet was made to prepare the specimen.

 The physical property evaluation was performed according to the above test items, except that the evaluation was performed by performing a working temperature of 121 ° C. and working time for 168 hours when evaluating heating loss. Mixed plasticizer composition of DOTP and TBC] was evaluated in the same manner, and the following items were further evaluated, and the results are shown in Tables 21 and 22, and the heat resistance test results are shown in FIG. 3.

<Additional test item>

Tensile residual

Measurements were made in the same manner as the tensile strength measurement described above, and the specimens used were exposed at 121 ° C. for 168 hours.

Elongation

It was measured in the same manner as the elongation measuring method described above, and the specimen used was a specimen exposed at 121 ° C. for 168 hours.

Cold resistance

Five fabricated specimens were left at a specific temperature for 3 minutes and then hit to measure the temperature when three of the five specimens were broken.

	Plasticizer	Shore "A"	Tensile Strength (kg / cm 2 )	Tensile Residual (%)	% Elongation	Elongation Retention (%)	Performance loss (%)	Heating loss (%)	Cold resistance (℃)	Heat resistance (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
Comparative Example 10	DIDP	87.5	175.6	94.5	317.9	91.3	0.99	8.36	-25.5	49.18
Comparative Example 11	DINIP	88.0	181.3	94.9	310.2	89.5	1.60	10.49	-28.5	47.02

As shown in Table 21, when comparing the Examples 17-1 to 17-3 and Comparative Examples 10 and 11 which is a DIDP or DINIP plasticizer composition as a conventional product, the plasticizer composition of Examples It can be confirmed that it is better or equivalent than the comparison. In particular, the cold resistance is almost the same level as the existing product, but it can be seen that the heat resistance is significantly improved.

On the other hand, as a result of the thermal stability test, referring to the image of Figure 3, in the case of Comparative Examples 10 and 11 of the existing product can be confirmed that it is vulnerable to blacking due to heat, but there is no change when a predetermined amount of epoxidized oil is added You can see that. That is, when epoxidized oil is added together with the citrate compound to improve the physical properties of plasticizer products such as DIDP or DINIP, it was confirmed that the thermal stability can be maintained and improved.

Experimental Example 6: Comparison with Acetyl Citrate Compound

In order to compare the difference between the properties of the citrate-based compound and the case of not including the acetyl group, acetyl 2-ethylhexyl citrate and DOTP in Examples 1-2, 2-2 and 5-2 and Comparative Example 12 A plasticizer composition mixed with was used as an experimental specimen. Specimen fabrication and physical property evaluation are described in [1. Mixed plasticizer composition of DOTP and TBC], and the results are shown in Table 22 below.

	Plasticizer	Shore "A"	Tensile Strength (kg / cm 2 )	% Elongation	Performance loss (%)	Heating 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
Comparative Example 12	DOTP + ATOC (70:30)	91.2	237.9	284.6	0.25	0.54

As shown in Table 22, when acetyl 2-ethylhexyl citrate is mixed, the hardness is greatly increased, and the plasticization efficiency, which is a physical property required for the plasticizer product, may be deteriorated, and the elongation characteristics are also deteriorated. It was confirmed. As a result, economic and process losses can also occur due to the need for more plasticizers compared to other products, which may adversely affect product quality depending on the presence or absence of an acetyl group. Able to know.

Although the preferred embodiments of the present invention have been described in detail above, the scope of the present invention is not limited thereto, and various modifications and improvements of those skilled in the art using the basic concepts of the present invention defined in the following claims are also provided. It belongs to the scope of rights.

Claims (20)

1. Terephthalate-based materials; And citrate compounds;

   The weight ratio of the terephthalate-based material and citrate-based compound is 99: 1 to 1:99 plasticizer composition.
2. The method of claim 1,

   Plasticizer composition of the weight ratio of the terephthalate-based material and citrate-based compound is 95: 5 to 50:50.
3. The method of claim 2,

   The weight ratio of the terephthalate-based material and citrate-based compound is 95: 5 to 60:40 plasticizer composition.
4. The method of claim 1,

   The terephthalate-based material is di (2-ethylhexyl) terephthalate (DEHTP or DOTP), diisononyl terephthalate (DINTP), dibutyl terephthalate (DBTP), butyl isononyl terephthalate (BINTP), butyl ( A plasticizer composition in which a single compound or a mixture of one or more compounds selected from the group consisting of 2-ethylhexyl) terephthalate (BEHTP or BOTP) and (2-ethylhexyl) isononyl terephthalate (EHINTP or OINTP) is mixed.
5. The method of claim 4, wherein

   And wherein said single compound is di (2-ethylhexyl) terephthalate or diisononyl terephthalate.
6. The method of claim 4, wherein

   The mixture is a first mixture of di (2-ethylhexyl) terephthalate, butyl (2-ethylhexyl) terephthalate and dibutyl terephthalate, or

   Or a second mixture of diisononyl terephthalate, butylisononyl terephthalate and dibutyl terephthalate,

   A plasticizer composition wherein di (2-ethylhexyl) terephthalate, (2-ethylhexyl) isononyl terephthalate and diisononyl terephthalate are mixed third mixtures.
7. The method of claim 6,

   The first mixture is

   Di (2-ethylhexyl) terephthalate 3.0 to 99.0 mol%;

   Butyl (2-ethylhexyl) terephthalate 0.5-96.5 mol% and

   Plasticizer composition comprising dibutyl terephthalate 0.5 to 96.5 mol%.
8. The method of claim 6,

   The second mixture is

   Diisononyl terephthalate 3.0 to 99.0 mol%;

   Butylisononyl terephthalate 0.5 to 96.5 mol% and

   Plasticizer composition comprising dibutyl terephthalate 0.5 to 96.5 mol%.
9. The method of claim 6,

   The third mixture is

   Di (2-ethylhexyl) terephthalate 3.0 to 99.0 mol%;

   0.5 to 96.5 mol% (2-ethylhexyl) isononyl terephthalate and

   Plasticizer composition comprising; diisononyl terephthalate 0.5 to 96.5 mol%.
10. The method of claim 1,

    The citrate compound is a plasticizer composition comprising any one selected from the group consisting of 4 to 9 carbon atoms of the mixed alkyl substituted citrate compound and 4 to 9 carbon atoms of the non-hybrid alkyl substituted citrate compound.
11. The method of claim 1,

    The citrate compound is a non-hybrid alkyl substituted citrate compound having 4 to 9 carbon atoms,

    Plasticizer composition of the alkyl group having 4 to 9 carbon atoms of the citrate compound is a straight chain or branched chain.
12. The method of claim 1,

    A plasticizer composition further comprising an epoxidized oil.
13. The method of claim 12,

    The plasticizer composition of the epoxidized oil is 1 to 100 parts by weight relative to 100 parts by weight of the plasticizer composition.
14. The method of claim 12,

    The epoxidized oil is epoxidized soybean oil, epoxidized castor oil, epoxidized linseed oil, epoxidized palm oil, epoxidized stearic acid plasticizer composition comprising at least one selected from the group consisting of acid), epoxidized oleic acid, epoxidized tall oil and epoxidized linoleic acid.
15. Preparing a terephthalate-based material and a citrate-based compound; And

    And blending the terephthalate-based material and the citrate-based compound in a weight ratio of 99: 1 to 1:99 to obtain a plasticizer composition.

    The terephthalate-based material is a method for producing a plasticizer composition is a single compound or a mixture.
16. The method of claim 15,

    When the terephthalate-based material is a single compound,

    Method for producing a plasticizer composition to prepare a terephthalate compound through a direct esterification reaction of at least one alcohol selected from the group consisting of 2-ethylhexyl alcohol, isononyl alcohol, butyl alcohol and isobutyl alcohol and terephthalic acid; .
17. The method of claim 15,

    When the terephthalate-based material is a mixture,

    Direct esterification reaction of at least one alcohol selected from the group consisting of 2-ethylhexyl alcohol, isononyl alcohol, butyl alcohol and isobutyl alcohol with terephthalic acid; or

    A terephthalate compound through a trans esterification reaction of any one of terephthalate selected from di (2-ethylhexyl) terephthalate or diisononyl terephthalate and any alcohol selected from butyl alcohol or isobutyl alcohol; The manufacturing method of a plasticizer composition to manufacture.
18. 100 parts by weight of resin; And 5 to 150 parts by weight of the plasticizer composition of claim 1.
19. The method of claim 18,

    The resin is a resin composition of at least one member selected from the group consisting of ethylene vinyl acetate, polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyurethane, and thermoplastic elastomer.
20. The method of claim 18,

    The resin composition is a resin composition which is a material of at least one product selected from the group consisting of electric wires, flooring materials, automobile interior materials, films, sheets, wallpaper, and tubes.

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