KR101742434B1 - Plasticizer, resin composition and method for preparing them - Google Patents

Abstract

The present invention relates to a plasticizer composition, a resin composition, and a process for producing the same, which is suitable for use as a plasticizer of a resin composition and is excellent in transparency and tackiness while being environmentally friendly, and can improve basic properties such as tensile strength, elongation and hardness And a resin composition containing them can be provided.

Description

TECHNICAL FIELD [0001] The present invention relates to a plasticizer composition, a resin composition, and a process for producing the same. BACKGROUND ART [0002]

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

Typically, the plasticizer reacts with the polycarboxylic acid, such as phthalic acid and adipic acid, to form the corresponding ester. In consideration of domestic and foreign regulations of phthalate plasticizers harmful to humans, studies on plasticizer compositions that can replace phthalate plasticizers such as terephthalate, trimellitate, and other high molecular weight have continued.

In general, plasticizers are added with various additives such as fillers, stabilizers, pigments, anti-fogging agents, and resins such as polyvinyl chloride (PVC) to give various processing properties, and they are processed by extrusion molding, injection molding, calendering, , Pipes, flooring, wallpaper, sheets, artificial leather, tarpaulins, tapes and food packaging.

Currently, the market for plasticizers is developing environmentally friendly plasticizers due to the environmental issues related to phthalate plasticizers. Recently, the market for di (2-ethylhexyl) terephthalate (DEHTP) New products are being developed to overcome quality deficiencies such as plasticization efficiency and migration.

Therefore, by developing a product of a novel composition containing di (2-ethylhexyl) terephthalate or a novel composition containing di (2-ethylhexyl) terephthalate, a technique which can be applied optimally as a plasticizer for a vinyl chloride resin This is a situation that needs to be studied continuously.

On the other hand, wrap film for food packaging is required to have transparency to observe the food as it is, and elongation, tensile strength, releasability, heat loss, and tackiness to give ease in packaging. Currently, terephthalate-based, glyceride-based, and glycol-based plasticizers are used in the packaging market for food wrapping products. These products are used for replacing the existing adipate-based product, dioctyl adipate There is a demand for environmentally friendly products in the future, and it is necessary to study the development of a plasticizer product having environmentally friendly and satisfactory quality.

Accordingly, the inventors of the present invention have found that while continuing research on plasticizers, they can be used as wrapping films as eco-friendly materials capable of improving poor physical properties caused by structural limitations, and can be improved in tackiness and transparency and improved in basic properties such as tensile strength and elongation This improved plasticizer composition was confirmed and the present invention was completed.

That is, an object of the present invention is to provide a plasticizer which can improve physical properties such as plasticization efficiency, transparency, tensile strength, elongation, heat loss, releasability and tackiness required in prescriptions of sheets and films when used as a plasticizer of a resin composition A process for producing the same, and a resin composition containing the same.

According to an embodiment of the present invention, there is provided a terephthalate-based material; And a succinate-based compound, wherein the weight ratio of the terephthalate-based material to the succinate-based compound is from 1:99 to 99: 1.

The weight ratio of the terephthalate-based material to the succinate-based compound may be 95: 5 to 30:70.

The weight ratio of the terephthalate-based material to the succinate-based compound may be 90:10 to 50:50.

The terephthalate-based material may be selected from the group consisting of di (2-ethylhexyl) terephthalate (DEHTP), diisononyl terephthalate (DINTP), dibutyl terephthalate (DBTP), butyl isononyl terephthalate (BINTP) Ethylhexyl) terephthalate (BEHTP) and (2-ethylhexyl) isononyl terephthalate (EHINTP) or a mixture of two or more compounds.

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

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

Wherein the first mixture comprises from 3.0 to 99.0 mol% di (2-ethylhexyl) terephthalate; 0.5 to 96.5 mol% of butyl (2-ethylhexyl) terephthalate and 0.5 to 96.5 mol% of dibutyl terephthalate.

The second mixture comprises from 3.0 to 99.0 mol% diisononyl terephthalate; 0.5 to 96.5 mol% of butyl isononyl terephthalate and 0.5 to 96.5 mol% of dibutyl terephthalate.

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

The succinate-based compound may be a compound represented by the following formula (1).

[Chemical Formula 1]

In the formula (1), R ₁ and R ₂ are the same or different and are each independently a straight chain alkyl group or a branched chain alkyl group having 4 to 10 carbon atoms.

The succinate-based compound may include at least one member selected from the group consisting of di (2-ethylhexyl) succinate, diisononyl succinate, and di (2-propylheptyl) succinate.

According to another embodiment of the present invention, there is provided a method of manufacturing a semiconductor device, comprising: preparing a terephthalate-based material and a succinate-based compound; And blending the terephthalate-based material and the succinate-based compound in a weight ratio of 1:99 to 99: 1 to obtain a plasticizer composition, wherein the terephthalate-based material is a single compound or a mixture Is provided.

When the terephthalate-based material is a single compound, direct esterification reaction in which any one alcohol selected from the group consisting of 2-ethylhexyl alcohol, isononyl alcohol, butyl alcohol and isobutyl alcohol reacts with terephthalic acid, To produce a phthalate compound.

When the terephthalate-based material is a mixture, a direct esterification reaction in which terephthalic acid is reacted with at least two alcohols selected from the group consisting of 2-ethylhexyl alcohol, isononyl alcohol, butyl alcohol and isobutyl alcohol; Or di (2-ethylhexyl) terephthalate or diisononyl terephthalate, and any one alcohol selected from butyl alcohol or isobutyl alcohol are reacted with the terephthalate compound . ≪ / RTI >

According to another embodiment of the present invention, there is provided a method for manufacturing a thermoplastic elastomer composition, comprising the steps of: preparing a thermoplastic elastomer composition comprising at least one resin 100 selected from the group consisting of ethylene vinyl acetate, polyethylene, polypropylene, polyketone, polyvinyl chloride, polystyrene, polyurethane and thermoplastic elastomer And 5 to 150 parts by weight of the above-mentioned plasticizer composition with respect to parts by weight of the resin composition.

The resin composition may be applied to manufacture at least one selected from the group consisting of electric wire, flooring, automobile interior material, film, sheet, wallpaper and tube.

The plasticizer composition according to an embodiment of the present invention can provide excellent adhesive properties and transparency while ensuring environmental friendliness, and can provide excellent plasticizability, excellent properties such as tensile strength and elongation when used in a resin composition .

Hereinafter, the present invention will be described in detail.

First, the present invention has a technical feature to provide a plasticizer composition capable of improving poor physical properties caused by structural limitations.

According to one embodiment of the present invention, a plasticizer composition containing a terephthalate-based material can be provided. Specifically, the content of the terephthalate-based material is selected in 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 a terminal 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 may be selected from the group consisting of di (2-ethylhexyl) terephthalate (DEHTP), diisononyl terephthalate (DINTP), dibutyl terephthalate (DBTP), butyl isononyl terephthalate (BINTP) Ethylhexyl) terephthalate (BEHTPP), and (2-ethylhexyl) isonyl terephthalate (EHINTP), 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. When the terephthalate-based material is a mixture, three types of terephthalate- The first mixture may be a mixture of di (2-ethylhexyl) terephthalate, butyl (2-ethylhexyl) terephthalate and dibutyl terephthalate, diisononyl terephthalate, butyl (2-ethylhexyl) terephthalate, (2-ethylhexyl) isononyl terephthalate and diisononyl terephthalate is mixed with a second mixture of isononyl terephthalate and dibutyl terephthalate .

Specifically, the first to third mixtures may have a specific composition ratio, and the first mixture may include 3.0 to 99.0 mol% of di (2-ethylhexyl) terephthalate; From 0.5 to 96.5 mol% of butyl (2-ethylhexyl) terephthalate and from 0.5 to 96.5 mol% of dibutyl terephthalate, and the second mixture comprises from 3.0 to 99.0 mol% of diisononyl terephthalate; From 0.5 to 96.5 mol% of butyl isononyl terephthalate and from 0.5 to 96.5 mol% of dibutyl terephthalate, and the third mixture is from 3.0 to 99.0 mol% of di (2-ethylhexyl) terephthalate; 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 mixing composition ratio generated by the esterification reaction, and may be an intended composition ratio by further mixing specific compounds, and the mixing composition ratio may be appropriately adjusted to meet the desired physical properties.

According to an embodiment of the present invention, the plasticizer composition may further include a succinate-based compound, and the succinate-based compound may be a compound represented by the following general formula (2).

[Chemical Formula 1]

In the formula (1), R ₁ and R ₂ are the same or different and are each independently a straight chain alkyl group or a branched chain alkyl group having 4 to 10 carbon atoms.

Specifically, the succinate-based compound represented by the formula (1) may have an alkyl group at both terminals and may have both a straight chain and a branched chain, and may have 4 to 10 carbon atoms. R ₁ and R ₂ may be an alkyl group having the same number of carbon atoms as each other, but in some cases, different alkyl groups having different carbon numbers from each other or different branch types may be applied. In this case, .

That is, the compound represented by Formula 2 may be applied to both the hybrid succinate-based compound and the non-hybrid succinate-based compound, but may be an unsubstituted alkyl group having 6 to 10 carbon atoms or an alkyl group having 8 to 10 carbon atoms It may be preferred that an alkyl group is applied. In the above formula (2), R ₁ and R ₂ may be a 2-ethylhexyl group, an isononyl group or a 2-propylheptyl group, and accordingly the succinate compound may be di (2-ethylhexyl) Succinate, diisononyl succinate, di (2-propylheptyl) succinate, and the like.

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

Although the succinate-based compound is an environmentally friendly plasticizer, it may be a plasticizer suitable for PVC for food packaging materials. However, when applied as a single plasticizer, problems such as poor tensile strength, heat loss and transparency may be present. However, when di (2-ethylhexyl) terephthalate is mixed together as in the present invention, the tensile strength, elongation, weight loss, transparency and adhesiveness of di (2-ethylhexyl) It is possible to provide a plasticizer composition more suitable for food packaging materials.

In the present invention, the plasticizer composition may be prepared by a blending method. The blending method may be as follows.

The plasticizer composition may be prepared by preparing a terephthalate-based material and a succinate-based compound, and blending the terephthalate-based material and the succinate-based compound at a weight ratio of 1:99 to 99: 1, The phthalate-based material is characterized by being a single compound or a mixture.

When the terephthalate-based material is a single compound, direct esterification reaction in which any one alcohol selected from the group consisting of 2-ethylhexyl alcohol, isononyl alcohol, butyl alcohol and isobutyl alcohol reacts with terephthalic acid, Phthalate-based materials can be produced.

The direct esterification reaction may be carried out by adding terephthalic acid to an alcohol, adding a catalyst, and reacting in a nitrogen atmosphere; Removing unreacted alcohol and neutralizing the unreacted acid; And dehydration and filtration by vacuum distillation.

Also, the alcohol used in the blending process may be 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 process may be 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.

Examples of the catalyst used in the blending process include inorganic acid catalysts such as sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid, para toluenesulfonic acid, methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, , Metal oxides such as potassium chloride, cesium chloride, calcium chloride, iron chloride and aluminum phosphate, metal oxides such as heteropoly acid, natural / synthetic zeolite, cation and anion exchange resin, tetra alkyl titanate and polymers thereof It may be at least one selected. As a specific example, the catalyst may use tetraalkyl titanate.

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

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 direct esterification reaction described above. In the direct esterification reaction, two or more alcohols may be added and reacted Lt; / RTI >

Alternatively, when the terephthalate-based material is a mixture, any one terephthalate compound selected from di (2-ethylhexyl) terephthalate or diisononyl terephthalate, and any alcohol selected from butyl alcohol or isobutyl alcohol The terephthalate compound can be prepared through a transesterification reaction in which the compound is reacted.

The "trans-esterification reaction" used in the present invention means a reaction in which an alcohol and an ester react with each other as shown in Reaction Scheme 1 below to mutually exchange R "of the ester with R 'of alcohol as shown in Reaction Scheme 1 below:

[Reaction Scheme 1]

According to one embodiment of the present invention, when the trans-esterification reaction is carried out, the alkoxide of the alcohol attacks the carbon of the two ester (RCOOR ") groups present in the ester compound; When attacking the carbon of the " RCOOR "group; In the case where the reaction is unreacted and unreacted, three kinds of ester compositions may be produced by the number in three cases.

In addition, the trans-esterification reaction is advantageous in that it does not cause wastewater problems as compared with the esterification reaction between acid and alcohol, and can proceed under no catalyst, thereby solving the problems in using acid catalyst.

For example, di (2-ethylhexyl) terephthalate and butyl alcohol are reacted with di (2-ethylhexyl) terephthalate, butyl (2-ethylhexyl) terephthalate and dibutyl terephthalate , And the three terephthalates may be formed in amounts of 3.0 wt% to 70 wt%, 0.5 wt% to 50 wt%, and 0.5 wt% to 85 wt%, respectively, based on the total weight of the mixture And specifically may be formed in an amount of 10 wt% to 50 wt%, 0.5 wt% to 50 wt%, and 35 wt% to 80 wt%. 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 to be added may be 0.1 to 89.9 parts by weight, specifically 3 to 50 parts by weight, more specifically 5 to 40 parts by weight, based on 100 parts by weight of the terephthalate compound.

Since the mole fraction of the terephthalate compound involved in the trans-esterification reaction becomes larger as the amount of alcohol added is larger, the content of the two terephthalate compounds as the product in the mixture may increase , And the content of the terephthalate compound present unreacted may correspondingly decrease.

According to one embodiment of the present invention, the molar ratio of the reactant terephthalate compound to the alcohol is, for example, 1: 0.005 to 5.0, 1: 0.05 to 2.5, or 1: 0.1 to 1.0, There is an effect of obtaining an ester-based plasticizer composition having an excellent improvement effect.

However, the composition ratio of the mixture of the three kinds of terephthalate-based materials is not limited to the above-mentioned range, and any one of three kinds of terephthalates may be further added to change the composition ratio thereof. Same as.

According to one embodiment of the present invention, the trans-esterification reaction is carried out at a reaction temperature of 120 to 190, preferably 135 to 180, more preferably 141 to 179 for 10 minutes to 10 hours, 8 hours, more preferably 1 to 6 hours. The mixture which is a terephthalate-based material having a desired composition ratio within the above temperature and time range can be effectively obtained. At this time, the reaction time can be calculated from the point at which the temperature of the reactant is raised to the reaction temperature.

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

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

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

Further, after the trans-esterification reaction, distilling off the unreacted alcohol and a reaction by-product, for example, an ester compound represented by the general formula (3), may be further included.

The distillation may be, for example, a two-step distillation in which the alcohol and the reaction by-products are separated using a difference in breaking point.

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

The direct esterification reaction and the trans esterification reaction can also be used for producing the succinate-based compound described above. In this case, as in the case of the terephthalate-based material, the succinate-based compound may also be prepared in a predetermined proportion of the mixed composition, and the composition ratio of the mixture produced by adjusting the content of the alcohol as the reaction raw material may be controlled. In addition, when the succinate-based compound is directly produced through an esterification reaction or a transesterification reaction, the contents may be applied in the same manner as the application of the terephthalate-based material.

The plasticizer composition thus produced may be used in an amount of 5 to 150 parts by weight, 40 to 100 parts by weight, or 40 to 100 parts by weight, based on 100 parts by weight of the resin selected from the group consisting of ethylene vinyl acetate, polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyurethane and thermoplastic elastomer. To 50 parts by weight, to provide a resin composition which is effective both for compound prescription, sheet prescription and prescription of plastisol.

For example, the plasticizer composition can be applied to the production of wires, flooring materials, automobile interior materials, films, sheets, wallpaper or tubes.

Example

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail with reference to examples. However, the embodiments according to the present invention can be modified into various other forms, and the scope of the present invention should not be construed as being limited to the embodiments described below. The embodiments of the present invention are provided to enable those skilled in the art to more fully understand the present invention.

Manufacturing example  One: Of di (2-ethylhexyl) terephthalate  Produce

498.0 g of purified terephthalic acid (TPA), 1170 g of 2-ethylhexyl alcohol (2-EH) (TPA: 2) were added to a four-liter three liter reactor equipped with a stirrer, a condenser, a decanter, 1.54 g (0.31 part by weight based on 100 parts by weight of TPA) of a titanium-based catalyst (TIPT, tetraisopropyl titanate) was added as a catalyst, and the temperature was gradually raised to about 170 캜 . Generated water began to be generated at about 170 ° C and the ester reaction was continued for about 4.5 hours while the nitrogen gas was continuously supplied at a reaction temperature of about 220 ° C and at normal pressure. When the acid value reached 0.01, the reaction was terminated.

After completion of the reaction, distillation extraction is carried out under reduced pressure for 0.5 to 4 hours to remove unreacted raw materials. Steam extraction is carried out under reduced pressure for 0.5 to 3 hours using steam to remove unreacted raw materials to a certain level or lower, the reaction liquid temperature is cooled to about 90 캜, and neutralization treatment is performed using an alkali solution . Further, washing may be carried out, and then the reaction liquid is dehydrated to remove water. The filter material was added to the reaction liquid from which the water had been removed, stirred for a predetermined time, and filtered to obtain 1326.7 g (yield: 99.0%) of di (2-ethylhexyl) terephthalate.

Manufacturing example  2: DEHTP / BEHTP / DBTP  Preparation of TP mixture

2000 g of di (2-ethylhexyl) terephthalate obtained in Preparation Example 1 and 340 g of n-butanol (17 parts by weight based on 100 parts by weight of DEHTP) were charged into a reactor equipped with a stirrer, a condenser and a decanter, (DBTP), butyl (2-ethylhexyl) terephthalate (BEHTP) and di (2-ethylhexyl) terephthalate (DEHTP) were each trans- esterified at a reaction temperature of 4.0 By weight, 35.0% by weight and 61.0% by weight, based on the total weight of the composition.

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

Manufacturing example  3: Preparation of di (2-ethylhexyl) succinate

(Yield: 98%) of di (2-ethylhexyl) succinate (hereinafter referred to as DEHS) was obtained by using 354 g of succinic acid as a reaction raw material and 585 g of 2-ethylhexanol.

Manufacturing example  4: Preparation of di (2-propylheptyl) succinate

1172 g (yield: 98%) of di (2-propylheptyl) succinate (hereinafter referred to as DPHS) was finally obtained using 354 g of succinic acid as a reaction source and 712 g of 2-propylheptanol.

Manufacturing example  5: Diisononyl Succinate  Produce

(Yield: 98%) of diisononyl succinate (hereinafter referred to as DINS) was obtained by using 354 g of succinic acid and 649 g of isononyl alcohol as a reaction raw material.

Example  1-1

The di (2-ethylhexyl) terephthalate prepared in Preparation Example 1 and the DEHS prepared in Preparation Example 3 were mixed at a weight ratio of 50:50 to obtain a plasticizer composition.

Example  1-2

The di (2-ethylhexyl) terephthalate prepared in Preparation Example 1 and DEHS prepared in Preparation Example 3 were mixed at a weight ratio of 90:10 to obtain a plasticizer composition.

Example  1-3

The di (2-ethylhexyl) terephthalate prepared in Preparation Example 1 and the DEHS prepared in Preparation Example 3 were mixed at a weight ratio of 70:30 to obtain a plasticizer composition.

Example  1-4

The di (2-ethylhexyl) terephthalate prepared in Preparation Example 1 and the DEHS prepared in Preparation Example 3 were mixed at a weight ratio of 30:70 to obtain a plasticizer composition.

Example  1-5

The di (2-ethylhexyl) terephthalate prepared in Preparation Example 1 and the DINS prepared in Preparation Example 5 were mixed at a weight ratio of 30:70 to obtain a plasticizer composition.

Example  1-6

The di (2-ethylhexyl) terephthalate prepared in Preparation Example 1 and the DINS prepared in Preparation Example 5 were mixed at a weight ratio of 50:50 to obtain a plasticizer composition.

Example  1-7

The di (2-ethylhexyl) terephthalate prepared in Preparation Example 1 and the DPHS prepared in Preparation Example 4 were mixed at a weight ratio of 50:50 to obtain a plasticizer composition.

Example  2-1

The TP mixture prepared in Preparation Example 2 and the DEHS prepared in Preparation Example 3 were mixed at a weight ratio of 50:50 to obtain a plasticizer composition.

Example  2-2

The TP mixture prepared in Preparation Example 2 and the DEHS prepared in Preparation Example 3 were mixed at a weight ratio of 90:10 to obtain a plasticizer composition.

Example  2-3

The TP mixture prepared in Preparation Example 2 and the DEHS prepared in Preparation Example 3 were mixed at a weight ratio of 70:30 to obtain a plasticizer composition.

Example  2-4

The TP mixture prepared in Preparation Example 2 and the DEHS prepared in Preparation Example 3 were mixed at a weight ratio of 30:70 to obtain a plasticizer composition.

Example  2-5

The TP mixture prepared in Preparation Example 2 and the DINS prepared in Preparation Example 5 were mixed at a weight ratio of 30:70 to obtain a plasticizer composition.

Example  2-6

The TP mixture prepared in Preparation Example 2 and the DINS prepared in Preparation Example 5 were mixed at a weight ratio of 50:50 to obtain a plasticizer composition.

Example  2-7

The TP mixture prepared in Preparation Example 2 and the DPHS prepared in Preparation Example 4 were mixed at a weight ratio of 50:50 to obtain a plasticizer composition.

Comparative Example  One

DEHTP as a plasticizer: Product name GL300 of LG Chemical Co., Ltd. was used alone.

Comparative Example  2

The DEHS prepared in Preparation Example 2 was used alone as a plasticizer.

Comparative Example  3

The DPHS prepared in Preparation Example 3 was used alone as a plasticizer.

Comparative Example  4

DINS prepared in Preparation Example 4 was used alone as a plasticizer.

Comparative Example  5

As a plasticizer, AMG (Rikevita, acetylated monoglyceride), which is used in eco-friendly products, was used alone.

<Test items>

The above examples and comparative examples were evaluated according to the following test items.

Hardness measurement

ASTM D2240 was used to measure the shore hardness, 3T 10s, at 25 占 폚.

Measurement of tensile strength

A cross head speed was pulled at 200 mm / min (1T) using a UTM (manufacturer; Instron, model name: 4466) according to the ASTM D638 method, and the point at which the specimen was cut was measured . The tensile strength was calculated as follows:

Tensile strength (kgf / mm 2) = load value (kgf) / thickness (mm) x width (mm)

Elongation elongation rate

After pulling the cross head speed at 200 mm / min (1T) using the U.TM according to the ASTM D638 method, the point at which the specimen was cut was measured and the elongation was calculated as follows:

Elongation (%) = length after elongation / initial length x 100.

Measurement of migration loss

Test specimens having a thickness of 2 mm or more were obtained in accordance with KSM-3156. PS plates were attached to both surfaces of the test pieces, and a load of 1 kgf / cm ² was applied. The specimens were left in a hot air circulating oven (80 ° C) for 72 hours, taken out and cooled at room temperature for 4 hours. After removing the PS attached to both sides of the test piece, weights were measured before and after leaving in the oven, and the amount of loss of migration was calculated by the following equation.

(%) = (Initial weight of test piece at normal temperature-weight of test piece after leaving oven) / initial weight of test piece at room temperature} x 100

Measurement of volatile loss

The prepared specimens were worked at 80 DEG C for 72 hours, and the specimens were weighed.

Heat loss (weight%) = initial specimen weight - (80, weight of the specimen after 72 hours of operation) / initial specimen weight of 100.

transparency

The Haze value was measured using a Haze Meter.

Adhesion evaluation

The degree of excellent adhesion was evaluated by 5 scales, with 1 being excellent and 5 being poor.

Experimental Example  1: Specimen preparation and performance evaluation

The plasticizers of Examples 1-1 to 1-7 and Comparative Examples 1 to 5 were used as experimental specimens. In the preparation of the specimen, 52.5 parts by weight of a plasticizer, 22.5 parts by weight of ESO as an auxiliary stabilizer, 2.55 parts by weight of an antifogging agent and 1.8 parts by weight of a stabilizer (LTX 630 p) were mixed by hand mixing in 100 parts by weight of PVC, The mill was operated at 160 占 폚 for 4 minutes and a wrap film was prepared using a press at 165 for 2.5 minutes (low pressure) and 2 minutes (high pressure). The following physical property tests were carried out using the respective specimens and the results are summarized in Table 1 below.

Plasticizer Hardness
(Shore "A") Seal
burglar
kg / cm ² Elongation
(%) implementation
Loss
(%) heating
outage
(%) Haze
(%) Stickiness Example 1-1 DEHTP + DEHS
(50:50) 82.1 235.9 356.2 0.53 3.52 5.6 2 Examples 1-2 DEHTP + DEHS
(90:10) 84.0 248.7 361.3 0.32 1.25 3.2 2 Example 1-3 DEHTP + DEHS
(70:30) 83.1 241.2 360.4 0.45 2.13 3.5 2 Examples 1-4 DEHTP + DEHS
(30:70) 81.2 231.3 318.9 0.67 3.88 3.6 One Examples 1-5 DEHTP + DINS
(30:70) 83.0 245.6 356.7 0.78 1.43 8.6 One Examples 1-6 DEHTP + DINS
(50:50) 83.9 247.1 342.1 0.15 0.88 6.7 2 Examples 1-7 DEHTP + DPHS
(50:50) 82.8 236.6 348.9 0.62 1.12 4.8 2 Comparative Example 1 DEHTP 84.8 249.1 360.9 0.31 1.08 3.5 5 Comparative Example 2 DEHS
80.7 182.4 340.6 0.95 7.18 9.5 3 Comparative Example 3 DPHS
83.7 175.3 315.2 0.30 1.44 34.0 4 Comparative Example 4 DINS
82.5 173.4 334.0 1.02 2.05 14.6 3 Comparative Example 5 AMG
83.5 202.3 336.6 2.56 3.64 8.7 4

Referring to the above Table 1, Comparative Examples 2 to 5 were actually used as materials or products which can be used as plasticizers in PVC for wrap films as environmentally friendly plasticizers, even when the basic properties are lowered by emphasizing the environmental friendliness. Table 1 shows that the tensile strength and elongation characteristics are low, the adhesiveness is not excellent, the heat loss and the migration loss are significant, and thus the anti-icing property is not excellent. On the other hand, the results of the specimens of Examples 1-1 to 1-7, which were applied as mixed compositions with DEHTP, show that the adhesiveness and transparency are significantly superior to those of the comparative examples, and the elongation and tensile strength characteristics It was confirmed that the results are better than the examples and the anti-rusting property is also excellent.

In comparison with Comparative Example 1, which is an eco-friendly product used in general use, it is found that plasticization efficiency and adhesiveness are considerably improved, and in the case of using the plasticizers of Examples, a sheet or film having excellent physical properties Can be produced.

Accordingly, when a plasticizer composition emphasizing the existing environmentally friendly aspects is used, when the DEHTP product is mixed with a problem that the basic properties such as tensile strength and elongation can not be supported without excellent adhesiveness or transparency as in the present invention, It is confirmed that it can be solved by keeping the environment friendliness, but also it can support the basic properties and maintains excellent adhesion and transparency.

Experimental Example  2: Specimen preparation and performance evaluation

The plasticizers of Examples 2-1 to 2-7 and Comparative Examples 1 to 5 were used as experimental specimens. In the preparation of the specimen, 52.5 parts by weight of a plasticizer, 22.5 parts by weight of ESO as an auxiliary stabilizer, 2.55 parts by weight of an antifogging agent and 1.8 parts by weight of a stabilizer (LTX 630 p) were mixed by hand mixing in 100 parts by weight of PVC, The mill was operated at 160 占 폚 for 4 minutes and a wrap film was prepared using a press at 165 for 2.5 minutes (low pressure) and 2 minutes (high pressure). The following physical property tests were carried out using the respective specimens, and the results are summarized in Table 2 below.

Plasticizer Hardness
(Shore "A") Seal
burglar
kg / cm ² Elongation
(%) implementation
Loss
(%) heating
outage
(%) Haze
(%) Stickiness Example 2-1 TP mixing + DEHS
(50:50) 81.0 235.9 351.3 0.48 4.03 4.8 One Example 2-2 TP mixing + DEHS
(90:10) 80.9 242.3 350.8 0.35 1.76 3.0 2 Example 2-3 TP mixing + DEHS
(70:30) 81.0 240.7 348.2 0.42 2.51 3.2 One Examples 2-4 TP mixing + DEHS
(30:70) 80.8 233.5 345.2 0.83 4.45 3.1 2 Example 2-5 TP mixing + DINS
(30:70) 82.3 256.7 365.1 0.84 1.68 5.6 2 Examples 2-6 TP mixing + DINS
(50:50) 81.8 260.5 368.9 0.46 1.48 3.9 One Examples 2-7 TP mixing + DPHS
(50:50) 82.6 261.7 364.1 0.26 1.06 4.8 One Comparative Example 1 DEHTP 84.8 249.1 360.9 0.31 1.08 3.5 5 Comparative Example 2 DEHS
80.7 182.4 340.6 0.95 7.18 9.5 3 Comparative Example 3 DPHS
83.7 175.3 315.2 0.30 1.44 34.0 4 Comparative Example 4 DINS
82.5 173.4 334.0 1.02 2.05 14.6 3 Comparative Example 5 AMG
83.5 202.3 336.6 2.56 3.64 8.7 4

With reference to Table 2, Comparative Examples 2 to 5 are eco-friendly plasticizers that can be used as plasticizers in plastic films for wrap films, emphasizing environmental friendliness, and are actually used even when their basic properties are degraded. Table 2 shows that the tensile strength and elongation characteristics are low, the adhesiveness is not excellent, the heat loss and the transition loss are significant, and therefore, the anti-icing property is not excellent. On the other hand, the results of the specimens of Examples 2-1 to 2-7, which were applied as mixed compositions with the TP mixture of DEHTP / BEHTP / DBTP, show that the adhesiveness and transparency are significantly better than those of the comparative examples , Elongation and tensile strength were also better than those of the comparative examples, and the durability was also excellent.

In comparison with Comparative Example 1, which is an eco-friendly product used in general use, it is found that plasticization efficiency and adhesiveness are considerably improved, and in the case of using the plasticizers of Examples, a sheet or film having excellent physical properties Can be produced.

As a result, when the plasticizer composition which emphasizes the existing environment friendliness is used, the problem that the tensile strength or elongation, which is not a basic property, is not supported by the adhesive property or the transparency but is not supported by the TP mixture of DEHTP / BEHTP / DBTP It is confirmed that when it is mixed with the product, it can be solved by keeping the environment friendliness while maintaining the basic properties, and also maintaining excellent adhesiveness and transparency.

Claims (17)

Terephthalate-based materials; And a succinate based compound,
The weight ratio of the terephthalate-based material to the succinate-based compound is 1:99 to 99: 1,
The terephthalate-based material may be selected from the group consisting of di (2-ethylhexyl) terephthalate (DEHTP), diisononyl terephthalate (DINTP), dibutyl terephthalate (DBTP), butyl isononyl terephthalate (BINTP) Ethylhexyl) terephthalate (BEHTP) and (2-ethylhexyl) isononyl terephthalate (EHINTP or OINTP), or a mixture of two or more compounds,
Wherein the succinate-based compound is at least one selected from the group consisting of di (2-ethylhexyl) succinate, diisononyl succinate, and di (2-propylheptyl) succinate.
The method according to claim 1,
Wherein the weight ratio of the terephthalate-based material to the succinate-based compound is 95: 5 to 30:70.
3. The method of claim 2,
Wherein the weight ratio of the terephthalate-based material to the succinate-based compound is 90:10 to 50:50.
delete The method according to claim 1,
Wherein the single compound is di (2-ethylhexyl) terephthalate or diisononyl terephthalate.
The method according to claim 1,
The mixture may be a first mixture of di (2-ethylhexyl) terephthalate, butyl (2-ethylhexyl) terephthalate and dibutyl terephthalate,
Diisononyl terephthalate, butyl isononyl terephthalate, and dibutyl terephthalate,
Wherein the third mixture is a mixture of di (2-ethylhexyl) terephthalate, (2-ethylhexyl) isononyl terephthalate and diisononyl terephthalate.
The method according to claim 6,
The first mixture
3.0 to 99.0 mol% of di (2-ethylhexyl) terephthalate;
0.5 to 96.5 mol% of butyl (2-ethylhexyl) terephthalate and
0.5 to 96.5 mol% of dibutyl terephthalate.
The method according to claim 6,
The second mixture
3.0 to 99.0 mol% of diisononyl terephthalate;
0.5 to 96.5 mol% of butyl isonyl terephthalate and
0.5 to 96.5 mol% of dibutyl terephthalate.
The method according to claim 6,
The third mixture
3.0 to 99.0 mol% of di (2-ethylhexyl) terephthalate;
0.5 to 96.5 mol% of (2-ethylhexyl) isononyl terephthalate and
0.5 to 96.5 mol% of diisononyl terephthalate.
delete delete Preparing a terephthalate-based material and a succinate-based compound; And
And blending the terephthalate-based material and the succinate-based compound at a weight ratio of 1:99 to 99: 1 to obtain a plasticizer composition,
The terephthalate-based material may be selected from the group consisting of di (2-ethylhexyl) terephthalate (DEHTP), diisononyl terephthalate (DINTP), dibutyl terephthalate (DBTP), butyl isononyl terephthalate (BINTP) Ethylhexyl) terephthalate (BEHTP) and (2-ethylhexyl) isononyl terephthalate (EHINTP or OINTP), or a mixture of two or more compounds,
Wherein the succinate-based compound is at least one selected from the group consisting of di (2-ethylhexyl) succinate, diisononyl succinate, and di (2-propylheptyl) succinate.
13. The method of claim 12,
When the terephthalate-based material is a single compound,
Wherein the terephthalate compound is prepared by a direct esterification reaction in which terephthalic acid is reacted with any one alcohol selected from the group consisting of 2-ethylhexyl alcohol, isononyl alcohol, butyl alcohol and isobutyl alcohol. Way.
13. The method of claim 12,
When the terephthalate-based material is a mixture,
A direct esterification reaction in which terephthalic acid is reacted with at least two alcohols selected from the group consisting of 2-ethylhexyl alcohol, isononyl alcohol, butyl alcohol and isobutyl alcohol; or
Esterification reaction in which any one terephthalate selected from di (2-ethylhexyl) terephthalate or diisononyl terephthalate is reacted with any one alcohol selected from butyl alcohol or isobutyl alcohol is reacted with the terephthalate compound By weight based on the total weight of the composition.
100 parts by weight of a resin; And 5 to 150 parts by weight of the plasticizer composition of claim 1.
16. The method of claim 15,
Wherein the resin is at least one selected from the group consisting of ethylene-vinyl acetate, polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyurethane and thermoplastic elastomer.
16. The method of claim 15,
Wherein the resin composition is applied to the production of at least one selected from the group consisting of electric wire, flooring, automobile interior material, film, sheet, wallpaper and tube.