KR102803921B1 - Plasticizer Composition and Vinyl Chloride Based Resin Composition Comprising the Same - Google Patents

Abstract

The present invention relates to a plasticizer composition comprising an isophthalate-based ester compound comprising at least one selected from the group consisting of di(2-ethylhexyl)isophthalate and diisononyl isophthalate; and a cyclohexane-based ester compound comprising at least one selected from the group consisting of di(2-ethylhexyl)cyclohexane-1,3-dicarboxylate, di(2-ethylhexyl)cyclohexane-1,4-dicarboxylate, and di(2-ethylhexyl)cyclohexane-1,2-dicarboxylate; and a vinyl chloride-based resin composition comprising the same.

Description

Plasticizer composition and vinyl chloride based resin composition comprising the same {Plasticizer Composition and Vinyl Chloride Based Resin Composition Comprising the Same}

The present invention relates to a plasticizer composition and a vinyl chloride-based resin composition comprising the same.

Plasticizers can impart various processing properties to resins such as polyvinyl chloride resins by mixing various additives such as stabilizers, fillers, blowing agents, pigments, and viscosity modifiers. Polyvinyl chloride resins are used in various products such as flooring, wallpaper, and sheets, and for this purpose, an appropriate plasticizer must be used considering plasticization efficiency, low-temperature flexibility, and sol viscosity.

Among the currently used plasticizers, some phthalate products, including dioctyl phthalate, are subject to environmental regulations in various product groups due to environmental hormone problems that disrupt the endocrine system, and this trend is expanding the development and use of eco-friendly plasticizers.

For example, di(2-ethylhexyl) phthalate, one of the commercial plasticizers, is a phthalic acid plasticizer, but it has the problems of high viscosity and poor flexibility at low temperatures. In addition, although di(2-ethylhexyl) terephthalate has the advantages of being environmentally friendly and having a somewhat low viscosity, its use is limited because it does not have excellent low-temperature flexibility.

Accordingly, there is a high demand for plasticizers that have low human toxicity and superior properties to existing commercial plasticizers.

Republic of Korea Patent Publication No. 10-2016-0113034

The present invention seeks to provide a plasticizer composition and a vinyl chloride resin composition comprising the same. Specifically, the present invention seeks to provide a plasticizer composition which is environmentally friendly and has excellent physical properties such as plasticization efficiency, low-temperature flexibility, and sol viscosity, and a vinyl chloride resin composition comprising the same.

One embodiment of the present invention provides a plasticizer composition comprising: an isophthalate-based ester compound comprising at least one selected from the group consisting of di(2-ethylhexyl)isophthalate and diisononyl isophthalate; and a cyclohexane-based ester compound comprising at least one selected from the group consisting of di(2-ethylhexyl)cyclohexane-1,3-dicarboxylate, di(2-ethylhexyl)cyclohexane-1,4-dicarboxylate, and di(2-ethylhexyl)cyclohexane-1,2-dicarboxylate.

Another embodiment of the present invention provides a vinyl chloride-based resin composition comprising the plasticizer composition.

Another embodiment of the present invention provides a resin molded product comprising the vinyl chloride-based resin composition.

The plasticizer composition according to one embodiment of the present invention has the advantage of being able to improve physical properties such as excellent plasticization efficiency, low-temperature flexibility, and/or sol viscosity when applied to a resin composition, particularly a vinyl chloride-based resin composition. Furthermore, the plasticizer composition according to one embodiment of the present invention has the advantage of being free from the environmental hormone problem that is a problem in existing phthalate-based plasticizers.

In this specification, when a part is said to "include" a certain component, this does not mean that it excludes other components, but rather that it may include other components, unless otherwise specifically stated.

In this specification, the unit “parts by weight” may mean the weight ratio between each component.

In this specification, “A and/or B” means “A and B, or A or B.”

The present inventors conducted research on a plasticizer that does not have environmental hormone problems and can implement properties equivalent to or superior to those of existing phthalate-based plasticizers, and as a result, confirmed that excellent plasticizer efficacy can be implemented when an isophthalate-based ester compound and a cyclohexane-based ester compound are applied simultaneously, and completed the present invention.

Hereinafter, the present invention will be described in detail.

One embodiment of the present invention relates to a plasticizer composition, comprising: an isophthalate-based ester compound comprising at least one selected from the group consisting of di(2-ethylhexyl)isophthalate and diisononyl isophthalate; and a cyclohexane-based ester compound comprising at least one selected from the group consisting of di(2-ethylhexyl)cyclohexane-1,3-dicarboxylate, di(2-ethylhexyl)cyclohexane-1,4-dicarboxylate, and di(2-ethylhexyl)cyclohexane-1,2-dicarboxylate.

The plasticizer composition according to the present invention is characterized by containing both an isophthalate-based ester compound and a cyclohexane-based ester compound. Specifically, the plasticizer composition according to the present invention may not contain a phthalate-based compound and/or a terephthalate-based compound, in addition to the isophthalate-based ester compound and the cyclohexane-based ester compound. Through this, the plasticizer composition according to the present invention can be free from environmental hormone problems, and further, can improve physical properties required for a plasticizer, such as plasticization efficiency, low-temperature flexibility, and/or sol viscosity.

According to one embodiment of the present invention, the weight ratio of the isophthalate-based ester compound and the cyclohexane-based ester compound may be 20:80 to 80:20. Specifically, the weight ratio of the isophthalate-based ester compound and the cyclohexane-based ester compound may be 30:70 to 70:30, or 40:60 to 60:40. Within the above weight ratio range, the plasticizer composition may exhibit improved plasticization efficiency when applied to a resin, and may implement improved low-temperature flexibility.

According to one embodiment of the present invention, the method for producing the isophthalate-based ester compound can be produced through an esterification reaction of a substance containing a hydroxyl group, for example, 2-ethylhexyl alcohol, and isophthalic acid in the presence of a catalyst. However, the present invention is not limited thereto, and the method for producing the isophthalate-based ester compound can be produced using materials and methods known in the art.

According to one embodiment of the present invention, the cyclohexane-based ester compound may be di(2-ethylhexyl)cyclohexane-1,3-dicarboxylate.

According to one embodiment of the present invention, the method for producing the cyclohexane-based ester compound can be produced through an esterification reaction between a substance containing a hydroxyl group, for example, 2-ethylhexane, and a cyclohexane-based substance, for example, 1,3-cyclohexane dicarboxylic acid, in the presence of a catalyst. However, the present invention is not limited thereto, and the method for producing the cyclohexane-based ester compound can be produced using materials and methods known in the art.

According to one embodiment of the present invention, the plasticizer composition may include di(2-ethylhexyl)isophthalate and di(2-ethylhexyl)cyclohexane-1,3-dicarboxylate. More specifically, the plasticizer composition may include only di(2-ethylhexyl)isophthalate and di(2-ethylhexyl)cyclohexane-1,3-dicarboxylate as plasticizer components.

Another embodiment of the present invention provides a vinyl chloride-based resin composition comprising the plasticizer composition.

According to one embodiment of the present invention, in the vinyl chloride-based resin composition, the content of the plasticizer composition may be 30 parts by weight or more and 150 parts by weight or less with respect to 100 parts by weight of the vinyl chloride-based resin composition. Specifically, the content of the plasticizer composition may be 30 parts by weight or more and 120 parts by weight or less, 30 parts by weight or more and 100 parts by weight or less, 30 parts by weight or more and 80 parts by weight or less, 40 parts by weight or more and 70 parts by weight or less, or 50 parts by weight or more and 60 parts by weight or less with respect to 100 parts by weight of the vinyl chloride-based resin composition. When the content of the plasticizer composition is less than the above range, the Shore A hardness and sol viscosity of the vinyl chloride-based resin composition may become excessively high, thereby reducing flexibility, and when it exceeds the above range, a problem of the plasticizer component being eluted to the outside of the vinyl chloride-based resin composition and/or a molded article thereof may occur.

Another embodiment of the present invention provides a resin molded product comprising the above-described vinyl chloride-based resin composition. Specifically, the resin molded product may be a wire, a flooring material, an automobile interior material, a film, a sheet, wallpaper, or a tube.

As described above, since the plasticizer composition according to the present invention has a human-friendly characteristic, the resin molded product can be free from the problem of human harm due to the elution of environmental hormones, and has the advantage of being molded with high processability.

Hereinafter, the present invention will be described in detail by way of examples in order to specifically explain the present invention. However, the examples according to the present invention may be modified in various different forms, and the scope of the present invention is not construed as being limited to the examples described below. The examples in this specification are provided to more completely explain the present invention to a person having average knowledge in the art.

[Manufacturing Example 1]

In a four-necked round-bottom flask equipped with a stirrer and a condenser, 170 g of isophthalic acid and 400 g of 2-ethylhexyl alcohol were placed, 0.58 g of a tetraisopropyl titanate catalyst was added, and esterification reaction was performed under a nitrogen atmosphere. The reaction was performed until the temperature reached approximately 220°C and no more effluent was generated. Then, unreacted substances were removed through depressurization, neutralization, and washing processes, thereby producing di(2-ethylhexyl)isophthalate (DOIP).

[Manufacturing Example 2]

In a four-necked round-bottom flask equipped with a stirrer and a condenser, 150 g of 1,3-cyclohexane dicarboxylic acid and 340 g of 2-ethylhexanol were placed, 0.45 g of tetraisopropyl titanate catalyst was added, and esterification reaction was performed under a nitrogen atmosphere. The reaction was performed until the temperature reached about 220°C and no more effluent was generated. Then, unreacted substances were removed through depressurization, neutralization, and water washing processes, thereby producing di(2-ethylhexyl)cyclohexane-1,3-dicarboxylate (1,3-DEHCH).

[Examples 1 to 4]

Di(2-ethylhexyl)isophthalate (DOIP) obtained in Manufacturing Example 1 and di(2-ethylhexyl)cyclohexane-1,3-dicarboxylate (1,3-DEHCH) obtained in Manufacturing Example 2 were mixed in a weight ratio as shown in Table 1 below to prepare a plasticizer composition.

Then, 100 parts by weight of polyvinyl chloride resin, 50 parts by weight of the above plasticizer composition, and 2 parts by weight of a Ba-Zn-based stabilizer were mixed, and then the mixture was worked at about 170° C. for about 5 minutes using a roll mill, and then pressed at about 185° C. for about 6 minutes to produce a polyvinyl chloride sheet, and its Shore A hardness, plasticization efficiency, and glass transition temperature were measured.

In addition, 100 parts by weight of polyvinyl chloride resin and 60 parts by weight of the plasticizer composition were mixed for about 10 minutes to prepare a plastisol, and its sol viscosity was measured.

[Comparative examples 1 and 2]

In order to compare the performance of the plasticizer composition according to the example with that of existing plasticizer products, di(2-ethylhexyl) phthalate (DEHP, Sigma Aldrich) and di(2-ethylhexyl) terephthalate (DOTP, Sigma Aldrich) were prepared in the same weight as the plasticizer composition according to the example.

Then, 100 parts by weight of polyvinyl chloride resin, 50 parts by weight of the above plasticizer composition, and 2 parts by weight of a Ba-Zn-based stabilizer were mixed, and then the mixture was worked at about 170° C. for about 5 minutes using a roll mill, and then pressed at about 185° C. for about 6 minutes to produce a polyvinyl chloride sheet, and its Shore A hardness, plasticization efficiency, and glass transition temperature were measured.

In addition, 100 parts by weight of polyvinyl chloride resin and 60 parts by weight of the plasticizer composition were mixed for about 10 minutes to prepare a plastisol, and its sol viscosity was measured.

[Comparative examples 3 and 4]

Di(2-ethylhexyl)isophthalate (DOIP) obtained in Manufacturing Example 1 and di(2-ethylhexyl)cyclohexane-1,3-dicarboxylate (1,3-DEHCH) obtained in Manufacturing Example 2 were prepared in the same weight as the plasticizer composition according to the example.

Then, 100 parts by weight of polyvinyl chloride resin, 50 parts by weight of the above plasticizer composition, and 2 parts by weight of a Ba-Zn-based stabilizer were mixed, and then the mixture was worked at about 170° C. for about 5 minutes using a roll mill, and then pressed at about 185° C. for about 6 minutes to produce a polyvinyl chloride sheet, and its Shore A hardness, plasticization efficiency, and glass transition temperature were measured.

In addition, 100 parts by weight of polyvinyl chloride resin and 60 parts by weight of the plasticizer composition were mixed for about 10 minutes to prepare a plastisol, and its sol viscosity was measured.

[Comparative Example 5]

Di(2-ethylhexyl)cyclohexane-1,3-dicarboxylate (1,3-DEHCH) obtained in Manufacturing Example 2 and di(2-ethylhexyl)phthalate (DEHP, Sigma Aldrich), a conventional plasticizer product, were mixed in a weight ratio as shown in Table 1 below to prepare a plasticizer composition.

Then, 100 parts by weight of polyvinyl chloride resin, 50 parts by weight of the above plasticizer composition, and 2 parts by weight of a Ba-Zn-based stabilizer were mixed, and then the mixture was worked at about 170° C. for about 5 minutes using a roll mill, and then pressed at about 185° C. for about 6 minutes to produce a polyvinyl chloride sheet, and its Shore A hardness, plasticization efficiency, and glass transition temperature were measured.

In addition, 100 parts by weight of polyvinyl chloride resin and 60 parts by weight of the plasticizer composition were mixed for about 10 minutes to prepare a plastisol, and its sol viscosity was measured.

[Comparative Example 6]

Di(2-ethylhexyl)cyclohexane-1,3-dicarboxylate (1,3-DEHCH) obtained in Manufacturing Example 2 and di(2-ethylhexyl)terephthalate (DOTP, Sigma Aldrich), a conventional plasticizer product, were mixed in a weight ratio as shown in Table 1 below to prepare a plasticizer composition.

Then, 100 parts by weight of polyvinyl chloride resin, 50 parts by weight of the above plasticizer composition, and 2 parts by weight of a Ba-Zn-based stabilizer were mixed, and then the mixture was worked at about 170° C. for about 5 minutes using a roll mill, and then pressed at about 185° C. for about 6 minutes to produce a polyvinyl chloride sheet, and its Shore A hardness, plasticization efficiency, and glass transition temperature were measured.

In addition, 100 parts by weight of polyvinyl chloride resin and 60 parts by weight of the plasticizer composition were mixed for about 10 minutes to prepare a plastisol, and its sol viscosity was measured.

The compositions of the plasticizer compositions according to Examples 1 to 4 and Comparative Examples 1 to 6 and the physical properties of the examples applying the same are shown in Table 1 below.

Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Plasticizer composition DOIP
(weight) 80 60 40 20 100 1,3-DEHCH
(weight) 20 40 60 80 100 60 60 DEHP(by weight) 100 40 DOTP(by weight) 100 40 Properties of resin Shore A hardness 81.5 79.7 79.0 79.3 78.5 82.2 82.3 78.5 78.5 81.0 Plasticization
Efficiency 1.04 1.02 1.01 1.01 1.00 1.05 1.05 1.00 1.00 1.03 Glass transition temperature (℃) -33 -35 -37 -34 -20 -20 -27 -31 -26 -25 Sol viscosity (cPs) 4900 4400 4000 3500 6900 6000 5400 3100 4700 4400

- Shore A hardness: The hardness value was measured 15 seconds after the hardness tester needle was fully lowered into the 6T specimen using the method according to ASTM D2240. Three locations were tested for each specimen and the average value was calculated. The lower the hardness value, the better the flexibility was evaluated.

- Plasticization efficiency: Calculated using the hardness value with DEHP as the standard (1.00). A smaller number is considered to indicate better plasticization efficiency.

- Glass transition temperature (℃): Using a differential scanning calorimeter (DSC, TA Instruments), the glass transition temperature was measured by heating the sample to 100 ℃, rapidly cooling it to -100 ℃, and then heating it again at a rate of 20 ℃ per minute. The lower the glass transition temperature, the better the flexibility at low temperatures.

- Plastisol viscosity (cPs): The manufactured plastisol was aged at room temperature for 1 hour, and then the viscosity was measured using a Brookfield viscometer (spindle 63, 20 rpm).

According to the results in Table 1 above, when the plasticizer composition according to the example is applied to a polyvinyl chloride resin, it can be confirmed that it exhibits plasticization efficiency and flexibility equivalent to those of existing plasticizer products. In particular, it can be confirmed that the plasticizer composition according to the example exhibits a lower glass transition temperature than existing plasticizer products, thereby enabling improved low-temperature flexibility to be implemented, and it can be confirmed that the viscosity of the sol can be controlled depending on the composition ratio, so that the viscosity required for the resin can be easily implemented.

Furthermore, in Comparative Example 3 where DOIP was applied alone and Comparative Example 4 where 1,3-DEHCH was applied alone, the plasticization efficiency was lower than in the examples, and there was a problem that the glass transition temperature was higher than in the examples, resulting in low-temperature flexibility. In addition, in the case of Comparative Examples 5 and 6 where 1,3-DEHCH and an existing plasticizer product were applied together, it was confirmed that the examples had low plasticization efficiency and low low-temperature flexibility compared to the examples. Therefore, it was found that it was effective to simultaneously apply an isophthalate-based ester compound and a cyclohexane-based ester compound as a plasticizer composition, as in the examples, in order to secure low-temperature flexibility and plasticization efficiency.

Claims (4)

A plasticizer composition comprising di(2-ethylhexyl)isophthalate and di(2-ethylhexyl)cyclohexane-1,3-dicarboxylate in a weight ratio of 20:80 to 80:20. delete A vinyl chloride-based resin composition comprising a plasticizer composition according to claim 1. In claim 3,
A vinyl chloride resin composition, characterized in that the content of the plasticizer composition is 30 parts by weight or more and 150 parts by weight or less with respect to 100 parts by weight of the vinyl chloride resin composition.