KR102496350B1 - Plasticizer composition and vinylchloride resin composition comprising the same - Google Patents

Abstract

The present invention relates to an eco-friendly plasticizer composition with improved plasticizer transferability and heating loss, and a vinyl chloride-based resin composition comprising the same.

Description

Plasticizer composition and vinyl chloride-based resin composition comprising the same

The present invention relates to a plasticizer composition that is environmentally friendly, exhibits a fast gelling rate to improve processability, has a low heating loss and has excellent migration resistance, and a vinyl chloride-based resin composition comprising the same.

A vinyl chloride-based resin is a homopolymer of vinyl chloride and a copolymer containing 50% or more of vinyl chloride, and is one of general-purpose thermoplastic resins produced by suspension polymerization and emulsion polymerization. Among them, the polyvinyl chloride-based resin produced by emulsion polymerization is a plasticizer, a stabilizer, a filler, a blowing agent, a pigment, a viscosity depressant, and titanium dioxide (TiO ₂ ) and additives are mixed and processed into plastisol or granule form, and through coating molding, extrusion molding, injection molding, and calendar molding processing methods, flooring materials, wallpaper, tarpaulin, artificial leather, toys, and automobile parts are produced. It is used in a wide range of fields such as coating materials.

Examples of plasticizers conventionally used in vinyl chloride-based resin compositions include phthalate-based products such as DEHP (Di-2-EthylHexyl Phthalate), DINP (Di-IsoNonyl Phthalate), DIDP (Di-Iso-Decyl Phthalate), BBP (Butyl Benzyl Phthalate) ), DBP (Di-n-butyl phthalate), and the like. In particular, DIDP is mainly used as a plasticizer capable of securing characteristics such as tensile strength, elongation, plasticization efficiency, heating loss, and tensile and elongation residual rate for wire covering materials and automobile interior materials.

However, phthalate-based plasticizers are socially suspected as endocrine disrupters that interfere with or disrupt human hormones and are suspected of being endocrine disruptors, and regulations are underway. In recent years, there has been an increasing need to develop eco-friendly products that can replace phthalate-based plasticizers.

Accordingly, trioctyl trimellitate (TOTM) is used as a substitute for DIDP in the field of wire covering materials or automotive interior materials that must exhibit stable performance even at high temperatures. However, in the case of TOTM, since mellitic anhydride, which is a raw material, contains a small amount of phthalic anhydride, there is a possibility of containing DEHP in the finished product, which is not free from environmental problems.

In order to solve the above problem, Korean Patent Publication No. 2016-0141297 discloses a plasticizer composition containing a trimellitate-based material and an epoxidized oil. However, the plasticizer composition of the above literature has a problem in that plasticizer migration is poor, and the plasticizer leaks out of the vinyl chloride-based resin over time.

Therefore, it is required to develop a novel plasticizer composition that is environmentally friendly while exhibiting the physical properties of a previously used DIDP plasticizer.

Korean Patent Publication No. 2016-0141297

The present invention provides a plasticizer composition that is environmentally friendly, exhibits a fast gelling rate to improve processability, has a low heating loss, and has excellent migration resistance, and a vinyl chloride-based resin composition comprising the same.

In order to solve the above problems, the present invention provides a plasticizer composition comprising tri (2-ethylhexyl) cyclohexane-1,2,4-tricarboxylate, epoxidized oil, and a cyclohexane dicarboxylate-based compound do.

The plasticizer composition, based on 100 parts by weight of the plasticizer composition, 5 to 85 parts by weight of the tri (2-ethylhexyl) cyclohexane-1,2,4-tricarboxylate, 10 to 90 parts by weight of the epoxidized oil, and 4 to 15 parts by weight of the cyclohexane dicarboxylate-based compound.

The epoxidized oil is epoxidized soybean oil, epoxidized castor oil, epoxidized linseed oil, epoxidized palm oil, epoxidized stearate ), epoxidized oleate, epoxidized tall oil, and epoxidized linoleate.

The cyclohexane dicarboxylate-based compounds include di(2-ethylhexyl)cyclohexane-1,4-dicarboxylate, diisononylcyclohexane-1,2-dicarboxylate, di(2-ethylhexyl) ) from the group consisting of cyclohexane-1,2-dicarboxylate, butyl (2-ethylhexyl)cyclohexane-1,4-dicarboxylate, and dibutylcyclohexane-1,4-dicarboxylate It may be one or more selected species.

The cyclohexane dicarboxylate-based compound may be di(2-ethylhexyl)cyclohexane-1,4-dicarboxylate.

In one embodiment, the plasticizer composition, based on 100 parts by weight of the plasticizer composition, tri (2-ethylhexyl) cyclohexane-1,2,4-tricarboxylate 5 to 85 parts by weight, epoxy as the epoxidized oil 10 to 90 parts by weight of soybean oil, and 4 to 15 parts by weight of di(2-ethylhexyl)cyclohexane-1,4-dicarboxylate as the cyclohexane dicarboxylate-based compound.

In addition, the present invention provides a vinyl chloride-based resin composition containing the above plasticizer composition.

The vinyl chloride-based resin composition may include 30 to 200 parts by weight of the plasticizer composition based on 100 parts by weight of the vinyl chloride-based resin.

At this time, the polymerization degree of the vinyl chloride-based resin may be 800 to 1,700.

The vinyl chloride-based resin composition may further include at least one selected from the group consisting of a stabilizer, a filler, and a pigment.

In addition, the present invention provides a molded article containing the vinyl chloride-based resin composition.

The molded article may be a wire covering material, foam sheet, decoration sheet, wallpaper, sealant, or flooring material.

The plasticizer composition according to the present invention includes tri(2-ethylhexyl)cyclohexane-1,2,4-tricarboxylate, an epoxidized oil, and a cyclohexane dicarboxylate-based compound together, thereby providing excellent migration resistance and Shows heating loss characteristics.

Therefore, the vinyl chloride-based resin composition containing the plasticizer composition of the present invention can solve environmental problems, and does not cause loss due to migration or heating of plasticizer even at high temperatures, so it is suitable for automotive heat-resistant wire coatings, wire covering materials or automobile interior materials. can be used suitably.

Terms used in this specification are only used to describe exemplary embodiments, and are not intended to limit the present invention. Singular expressions include plural expressions unless the context clearly dictates otherwise.

Since the present invention can have various changes and various forms, specific embodiments will be exemplified and described in detail below. However, it should be understood that this is not intended to limit the present invention to the specific disclosed form, and includes all modifications, equivalents, and substitutes included in the spirit and scope of the present invention.

Hereinafter, according to specific embodiments of the present invention, a plasticizer composition, a vinyl chloride-based resin composition including the plasticizer composition, and a molded article will be described in more detail.

plasticizer composition

The plasticizer composition according to the present invention, due to the interaction of three specific types of plasticizers, is focused on the fact that it can greatly reduce the transferability and heating loss of the plasticizer while exhibiting excellent physical properties as a plasticizer.

The plasticizer composition according to one embodiment of the present invention includes tri(2-ethylhexyl)cyclohexane-1,2,4-tricarboxylate, an epoxidized oil, and a cyclohexane dicarboxylate-based compound.

The tri(2-ethylhexyl)cyclohexane-1,2,4-tricarboxylate (tri(2-ethylhexyl)cyclohexane-1,2,4-tricarboxylate (TEHCH) is a compound represented by Formula 1 below.

[Formula 1]

Compared to phthalate-based plasticizers, TEHCH has the advantage of less generation of volatile organic compounds, has the advantage of lower plasticizer transferability and lower heating loss, and has excellent properties.

However, when the TEHCH is used as a sole plasticizer, the gelling rate is very slow, so the processing temperature must be increased, and protrusions may occur due to a decrease in melting during production of the finished product. Accordingly, in the present invention, an epoxidized oil and a cyclohexane dicarboxylate-based compound are used together to compensate for this.

Specifically, the TEHCH may be used in an amount of 5 parts by weight or more, 20 parts by weight or more, 30 parts by weight or more, or 50 parts by weight or more, and 85 parts by weight or less, or 80 parts by weight or less, based on 100 parts by weight of the plasticizer composition. If the content of TEHCH is less than 5 parts by weight based on 100 parts by weight of the plasticizer composition, the effect of reducing plasticizer migration and heating loss cannot be obtained, and if it exceeds 80 parts by weight, a decrease in gelling rate and sol viscosity may occur.

The epoxidized oil is an epoxidized fatty acid alkyl ester prepared by epoxidizing a fatty acid alkyl ester. These epoxidized oils can exhibit effects of improving heat resistance, plasticization efficiency, absorption rate, and heating loss, and are excellent in economic efficiency.

Specifically, the epoxidized oil may be an epoxidized vegetable oil obtained by epoxidizing a vegetable fatty acid ester, for example, epoxidized soybean oil, epoxidized castor oil, epoxidized linseed oil oil), epoxidized palm oil, epoxidized stearate, epoxidized oleate, epoxidized tall oil, and epoxidized linoleate. One or more selected from the group may be used. Among them, epoxidized soybean oil may be preferable in view of price and ease of domestic supply and demand.

The epoxidized oil may be used in an amount of 10 parts by weight or more, or 15 parts by weight or more, and 90 parts by weight or less, 70 parts by weight or less, or 50 parts by weight or less, based on 100 parts by weight of the plasticizer composition. If the epoxidized oil is less than 10 parts by weight in 100 parts by weight of the plasticizer composition, heat resistance and heating loss characteristics may be deteriorated, and if it exceeds 90 parts by weight, the content of TEHCH and cyclohexane dicarboxylate-based compounds is relatively reduced, resulting in a decrease in heating loss Problems such as deterioration in properties and deterioration in migration resistance may occur.

The cyclohexane dicarboxylate-based compound is an ester derivative of cyclohexane-1,2-dicarboxylic acid, cyclohexane-1,3-dicarboxylic acid, or cyclohexane-1,4-dicarboxylic acid. , Specifically, di(2-ethylhexyl)cyclohexane-1,4-dicarboxylate (Di(2-ethylhexyl)cyclohexane-1,4-dicarboxylate; DEHCH), diisononylcyclohexane-1,2- Diisononyl cyclohexane-1,2-dicarboxylate (DINCH), Di(2-ethylhexyl)cyclohexane-1,2-dicarboxylate (Di(2-ethylhexyl)cyclohexane-1,2-dicarboxylate; DOCH), Butyl (2-ethylhexyl) cyclohexane-1,4-dicarboxylate (BEHCH), and dibutylcyclohexane-1,4-dicarboxylate It may be at least one selected from the group consisting of dibutyl cyclohexane-1,4-dicarboxylate (DBCH).

Among them, DEHCH is a compound represented by Formula 2 below, and has low viscosity at room temperature and low temperature, so that excellent coating properties can be realized, a gelling rate is fast, and foaming properties are excellent. In addition, generation of volatile organic compounds can be minimized compared to conventional phthalate-based plasticizers.

[Formula 2]

The cyclohexane dicarboxylate-based compound is preferably included in an amount of 4 to 15 parts by weight or 4 to 10 parts by weight based on 100 parts by weight of the plasticizer composition. When the amount of the cyclohexane dicarboxylate-based compound exceeds 15 parts by weight based on 100 parts by weight of the plasticizer composition, the gelling rate and foaming performance may be excellent, but the plasticizer transferability and heating loss may increase. In addition, if the content of the cyclohexane dicarboxylate-based compound is too small, less than 4 parts by weight based on 100 parts by weight of the plasticizer composition, the gelling rate may be lowered and the plasticization efficiency may be low, so it is preferable to satisfy the above range. do.

As described above, the plasticizer composition of the present invention simultaneously contains three types of tri(2-ethylhexyl)cyclohexane-1,2,4-tricarboxylate, epoxidized oil, and cyclohexane dicarboxylate-based compound. Accordingly, it not only exhibits excellent gelling rate and plasticization efficiency, but also exhibits plasticizer transitivity and low heating loss. Meanwhile, according to one embodiment of the present invention, the plasticizer composition may not include other plasticizer compounds other than the aforementioned TEHCH, epoxidized oil, and cyclohexane dicarboxylate-based compound.

The plasticizer composition according to one embodiment of the present invention, based on 100 parts by weight of the plasticizer composition, 5 to 85 parts by weight of tri (2-ethylhexyl) cyclohexane-1,2,4-tricarboxylate, the epoxidized oil It may include 10 to 90 parts by weight of epoxidized soybean oil, and 4 to 15 parts by weight of di(2-ethylhexyl)cyclohexane-1,4-dicarboxylate as the cyclohexane dicarboxylate-based compound.

In addition, the plasticizer composition according to one embodiment of the present invention, based on 100 parts by weight of the plasticizer composition, 50 to 85 parts by weight of tri(2-ethylhexyl)cyclohexane-1,2,4-tricarboxylate, the epoxy It may contain 10 to 50 parts by weight of epoxidized soybean oil as an oxidizing oil, and 4 to 10 parts by weight of di(2-ethylhexyl)cyclohexane-1,4-dicarboxylate as the cyclohexane dicarboxylate-based compound. there is.

The plasticizer composition of the present invention can be used in resin compositions such as polyvinyl chloride, polystyrene, polyurethane, polyethylene, polypropylene, silicone, modified silicone, ethylene vinyl acetate resin and thermoplastic elastomer, and has low heating loss and low plasticizer migration. It can be particularly suitably used for vinyl chloride-based resin compositions requiring heat resistance.

The plasticizer composition of the present invention exhibits excellent heating loss characteristics with a volatilization amount of 0.2% by weight or less, measured after being allowed to stand at 200 ° C. for 24 hours. Accordingly, there is no risk of deterioration in processability due to the reduction of plasticizer due to volatilization, and process stability can be improved by reducing the amount of fume generated during the process. The method for measuring heating loss may be embodied in an embodiment to be described later.

Vinyl chloride-based resin composition

According to another embodiment of the present invention, a vinyl chloride-based resin composition comprising a vinyl chloride-based resin and the plasticizer composition is provided.

More specifically, the vinyl chloride-based resin composition may include 30 to 200 parts by weight, or 40 to 70 parts by weight, or 50 to 70 parts by weight of the plasticizer composition based on 100 parts by weight of the vinyl chloride resin.

By including the plasticizer composition according to the present invention, the vinyl chloride-based resin composition can further improve plasticizer migration properties and heating loss characteristics. The vinyl chloride-based resin is polyvinyl chloride (PVC), and a polymerization degree of 800 to 1,700 may be used, but is not limited thereto.

Throughout the present specification, the vinyl chloride-based resin refers to a vinyl chloride-based monomer alone or a (co)polymer obtained by copolymerization of a vinyl chloride-based monomer and a copolymerizable comonomer thereof. In addition, it may be prepared by a polymerization method such as suspension polymerization, microsuspension polymerization, emulsion polymerization, or miniemulsion polymerization by mixing a suspending agent, a buffer, and a polymerization initiator.

Other monomers copolymerizable with the aforementioned vinyl chloride monomer include, for example, vinyl ester-based monomers including ethylene vinyl acetate monomers and vinyl propionate monomers; olefinic monomers including ethylene, propylene, isobutyl vinyl ether, and halogenated olefins; methacrylic acid ester-based monomers including methacrylic acid alkyl esters; maleic anhydride monomer; acrylonitrile monomer; styrene monomer; and halogenated polyvinylidene, etc., and a copolymer with vinyl chloride monomer may be prepared by mixing one or more of them. However, the present invention is not limited to the above-mentioned monomers, and according to the physical properties or uses of the vinyl chloride-based resin composition required during production, copolymers are generally formed through polymerization with vinyl chloride monomers in the technical field to which the present invention belongs. The monomers used to form may be used without particular limitation.

The vinyl chloride-based resin composition may further include at least one selected from the group consisting of an additive, for example, a stabilizer, a filler, and a pigment. The additive may be appropriately selected according to physical properties to be improved in the vinyl chloride-based resin composition.

The stabilizer is added for the purpose of preventing various physical property changes caused by separation of HCl from vinyl chloride-based resin to form a polyene structure, which is a chromophore, and cutting and cross-linking of the main chain. Ca-Zn-based compounds, K -Zn-based compounds, Ba-Zn-based compounds, organic Tin-based compounds; It includes at least one selected from the group consisting of a metallic soap-based compound, a phenol-based compound, a phosphoric acid ester-based compound, or a phosphorous acid ester-based compound. More specific examples of the stabilizer that can be used in the present invention are Ca-Zn-based compounds; K-Zn-based compounds; Ba-Zn-based compounds; organic Tin-based compounds such as mercaptide-based compounds, maleic acid-based compounds, or carboxylic acid-based compounds; metallic soap-based compounds such as Mg-stearate, Ca-stearate, Pb-stearate, Cd-stearate, or Ba-stearate; phenolic compounds; phosphoric acid ester compounds; Or a phosphorous acid ester-based compound, etc., which are optionally included depending on the purpose of use. In the present invention, it is particularly preferable to use a Ca-Zn-based compound.

The stabilizer is preferably included in an amount of 0.5 to 7 parts by weight, more preferably 1 to 4 parts by weight, based on 100 parts by weight of the vinyl chloride resin. If the content of the stabilizer is less than 0.5 parts by weight, there is a problem of poor thermal stability, and if it exceeds 7 parts by weight, there is a problem of poor processability.

The filler of the present invention is used for the purpose of improving productivity, dry touch, etc. of a vinyl chloride-based resin composition, and is composed of calcium carbonate, talc, titanium dioxide, kaolin, silica, alumina, magnesium hydroxide or clay. It includes any one or more selected from the group consisting of

In the vinyl chloride-based resin composition according to the present invention, the filler may be preferably included in an amount of 10 to 150 parts by weight, more preferably 50 to 130 parts by weight. When the filler is included in less than 50 parts by weight, there is a problem in that dimensional stability and economical efficiency are lowered, and when it is included in more than 130 parts by weight, there is a problem in that the foamed surface is not good and the processability is lowered.

The pigment may be titanium dioxide, carbon black, or a cadmium-based pigment. The pigment may be included in an amount of 0.1 to 10 parts by weight or 1 to 7 parts by weight based on 100 parts by weight of the vinyl chloride resin. If the pigment is included in an amount of less than 0.1 parts by weight, it is difficult to implement color, and if it exceeds 10 parts by weight, mechanical properties and the foamed surface may be deteriorated.

The vinyl chloride-based resin composition according to the present invention may be prepared by a method generally known in the art using a vinyl chloride-based resin, the plasticizer composition, and optionally an additive, and the method is not particularly limited.

The vinyl chloride-based resin composition exhibits a fast gelling rate to improve processability, exhibits a low heating loss, and has excellent migration resistance.

Specifically, the vinyl chloride-based resin composition according to the present invention has a plasticizer transferability of 0.5% by weight or less, 0.4% by weight or less, or 0.3% by weight or less, and the outflow of the plasticizer is significantly reduced to maintain excellent plasticizing effect, and the environment don't cause any problems

The method for measuring the transferability of the plasticizer may be embodied in Examples to be described later.

The vinyl chloride-based resin composition of the present invention can be suitably used in fields requiring heat resistance due to its excellent properties as described above. Specifically, the vinyl chloride-based resin composition may be used as wire covering materials, automobile interior materials, foam sheets, decorative sheets, flooring materials, wallpaper, mats, tarpaulins, sealants, artificial leather, toys, automobile underbody coating materials, and the like, and in particular, electric wire covering materials. , automobile interior materials, and the like.

Meanwhile, according to another aspect of the present invention, a molded article including the vinyl chloride-based resin composition is provided. The molded article may be prepared by adding additives such as a stabilizer, a filler, and/or a foaming agent to the vinyl chloride-based resin composition according to its use.

The molded product can be used as wire covering materials, automobile interior materials, foam sheets for automobiles, decorative sheets, flooring materials, wallpaper, mats, tarpaulins, sealants, artificial leather, toys, automobile lower coating materials, etc., and heat resistance due to excellent heat loss characteristics. It can be particularly suitably used for electric wire covering materials of automobiles and the like, automobile interior materials, etc., which require this.

Hereinafter, the present invention will be described in more detail by the following examples. However, the following examples are only for exemplifying the present invention, and the scope of the present invention is not limited only to these.

[Example]

<Preparation of plasticizer composition and vinyl chloride-based resin composition>

Examples 1 to 4

Tri(2-ethylhexyl)cyclohexane-1,2,4-tricarboxylate (TEHCH), epoxidized soybean oil (ESO, Songwon E-700), and di(2-ethylhexyl)cyclo A plasticizer composition was prepared by mixing hexane-1,4-dicarboxylate (DEHCH). The composition and content of the plasticizer are recorded in Table 1 below.

Based on 100 parts by weight of polyvinyl chloride, 50 parts by weight of the plasticizer composition prepared above, 10 parts by weight of Ca-Zn composite stabilizer (Songwon CZ-200), 20 parts by weight of CaCO ₃ filler (Omya-1T), carbon black ( C/B) 5 parts by weight were weighed and mixed with a mixer, and then kneaded using a roll mill to prepare a vinyl chloride-based resin composition.

Comparative Examples 1 to 8

A vinyl chloride resin composition was prepared in the same manner as in Example 1, except for using the plasticizer composition as shown in Table 1 below.

TEHCH content (parts by weight) ESO
Content (parts by weight) DEHCH content (parts by weight) etc Example 1 25 23 2 - Example 2 30 15 5 - Example 3 40 8 2 - Example 4 40 5 5 - Comparative Example 1 - - - DIDP
50 parts by weight Comparative Example 2 - - - TOTM
50 parts by weight Comparative Example 3 45 3 2 - Comparative Example 4 - 25 25 - Comparative Example 5 43 5 2 - Comparative Example 6 2 46 2 - Comparative Example 7 21 21 8 - Comparative Example 8 25 25 - -

< Experimental example >

With respect to the plasticizer compositions and vinyl chloride-based resin compositions prepared in Examples and Comparative Examples, plasticizer transferability and heating loss were evaluated as follows, and the results are shown in Table 1.

(1) plasticizer transferability

The evaluation of plasticizer transferability was performed as follows.

The prepared vinyl chloride-based resin composition was sequentially subjected to roll mill processing (170° C., 3 minutes) and press processing (180° C., 8 minutes) to prepare a 2 mm flat plate. The prepared flat plate was cut into a circular specimen having a diameter of about 4 cm. Oil absorbent paper made of polypropylene was placed on the top and bottom of the specimen, and left for 7 days at 60℃ under a load of 5kg to promote plasticizer migration. After the completion of the plasticizer transfer test, the weight change rate of the specimen and oil paper was measured.

The weight change rate of the specimen was calculated as [(weight change of specimen / weight of specimen before test) * 100], and the weight change rate of oil paper was calculated as [(weight change of oil paper / weight of oil paper before test) * 100] Calculated. The weight decrease of the specimen is the same as the weight increase of the oil paper, so in this experiment, the plasticizer transferability was evaluated only by the weight change rate of the specimen.

(2) heating loss

After the plasticizer compositions of Examples and Comparative Examples were allowed to stand at 200° C. for 24 hours, weight changes were measured.

Heating loss (%) = [(initial weight of plasticizer composition - weight of plasticizer composition after operation) / weight of initial plasticizer composition] x 100 was calculated.

(3) thermal stability

The roll mill processing sheet was cut into a strap shape of 15 mm Х 480 mm and mounted in a 190℃ Mathis Oven. The specimen mounted in the oven was set to be discharged out of the oven at a speed of 15 mm/5 minutes. The heat resistance time (minutes) was calculated through the length from the end of the test to the start of discoloration (length that is not carbonized, mm).

(4) gelling rate

54 g of the blended resin was put into a Brabender Mixer at 95 ° C and mixed for 10 minutes at 30 rpm. Resin gelling time was analyzed through torque change during mixer processing time.

Transitionability (%) Heat loss (%) thermal stability
(Time of discoloration, minutes) Gelling time (seconds) Example 1 0.20 0.20 102 282 Example 2 0.21 0.18 92 290 Example 3 0.25 0.18 82 315 Example 4 0.27 0.19 84 310 Comparative Example 1 0.12 0.20 92 320 Comparative Example 2 0.10 0.09 121 450 Comparative Example 3 0.19 0.15 91 423 Comparative Example 4 0.49 0.59 91 221 Comparative Example 5 0.18 0.15 93 442 Comparative Example 6 1.20 0.50 72 320 Comparative Example 7 0.57 0.23 98 310 Comparative Example 8 0.10 0.39 93 420

Referring to Table 2, the plasticizers of Examples 1 to 4 are tri(2-ethylhexyl)cyclohexane-1,2,4-tricarboxylate, epoxidized oil, and cyclohexane dicarboxylate-based compounds. Consisting of three components, it can be confirmed that it exhibits transferability and heating loss characteristics similar to DIDP and TOTM, and has excellent thermal stability and gelling rate. However, it can be confirmed from Comparative Examples 3 to 8 that the above effect cannot be achieved when any one of the three components is not included or when each component does not satisfy the content range of the present invention.

Claims (12)

A plasticizer composition comprising tri(2-ethylhexyl)cyclohexane-1,2,4-tricarboxylate, an epoxidized oil, and a cyclohexane dicarboxylate-based compound,
With respect to 100 parts by weight of the plasticizer composition,
5 to 85 parts by weight of the tri(2-ethylhexyl)cyclohexane-1,2,4-tricarboxylate,
10 to 90 parts by weight of the epoxidized oil, and
A plasticizer composition comprising 4 to 15 parts by weight of the cyclohexane dicarboxylate-based compound. delete According to claim 1,
The epoxidized oil is epoxidized soybean oil, epoxidized castor oil, epoxidized linseed oil, epoxidized palm oil, epoxidized stearate ), at least one plasticizer composition selected from the group consisting of epoxidized oleate, epoxidized tall oil, and epoxidized linoleate. According to claim 1,
The cyclohexane dicarboxylate-based compounds include di(2-ethylhexyl)cyclohexane-1,4-dicarboxylate, diisononylcyclohexane-1,2-dicarboxylate, di(2-ethylhexyl) ) from the group consisting of cyclohexane-1,2-dicarboxylate, butyl (2-ethylhexyl)cyclohexane-1,4-dicarboxylate, and dibutylcyclohexane-1,4-dicarboxylate One or more selected plasticizer compositions. According to claim 1,
The plasticizer composition of claim 1, wherein the cyclohexane dicarboxylate-based compound is di(2-ethylhexyl)cyclohexane-1,4-dicarboxylate. According to claim 1,
With respect to 100 parts by weight of the plasticizer composition,
5 to 85 parts by weight of tri(2-ethylhexyl)cyclohexane-1,2,4-tricarboxylate;
10 to 90 parts by weight of epoxidized soybean oil as the epoxidized oil, and
A plasticizer composition comprising 4 to 15 parts by weight of di(2-ethylhexyl)cyclohexane-1,4-dicarboxylate as the cyclohexane dicarboxylate-based compound. A vinyl chloride-based resin, and
A vinyl chloride-based resin composition comprising the plasticizer composition of any one of claims 1 and 3 to 6. According to claim 7,
A vinyl chloride-based resin composition comprising 30 to 200 parts by weight of the plasticizer composition based on 100 parts by weight of the vinyl chloride-based resin. According to claim 7,
The degree of polymerization of the vinyl chloride-based resin is 800 to 1,700 of the vinyl chloride-based resin composition. According to claim 7,
A vinyl chloride-based resin composition further comprising at least one selected from the group consisting of a stabilizer, a filler, and a pigment. A molded article comprising the vinyl chloride-based resin composition of claim 7. According to claim 11,
Molded articles that are wire covering materials, foam sheets, decorative sheets, wallpaper, sealants, or flooring materials.