ES2956465T3 - Plasticizer composition and resin composition that includes the same - Google Patents

Abstract

The present invention relates to a plasticizer composition comprising cyclohexane-1,4-diester material, an epoxidized alkyl ester composition and a citrate material, the plasticizer composition being environmentally friendly while having excellent stability. and basic physical properties. (Automatic translation with Google Translate, without legal value)

Description

DESCRIPTION

Plasticizer composition and resin composition that includes the same

Technical field

The present invention relates to a plasticizer composition and a resin composition including the same, and more particularly, to a plasticizer composition that is environmentally friendly and has high stability and excellent basic properties and to a resin composition that includes the same.

[Previous technique]

Conventionally, a plasticizer forms an ester through a reaction between an alcohol and a polycarboxylic acid such as phthalic acid or adipic acid. Furthermore, taking into account the national and international regulations for phthalate-based plasticizers harmful to humans, there is ongoing research on plasticizer compositions that can replace phthalate-based plasticizers such as terephthalate-based plasticizers, adipate and other polymers.

Meanwhile, in composite industries that require high heat resistance and low volatile loss as main desired physical properties, suitable plasticizers need to be used keeping in mind the desired physical properties. In the case of polyvinyl chloride (PVC) compounds used for electrical wires and cables, a PVC resin is mixed in combination with a third substance such as a plasticizer, a stabilizer, a pigment or the like depending on the properties required for the corresponding specifications, such as tensile strength, an elongation rate, plasticization efficiency, loss of volatiles, tensile retention and elongation, and the like.

In various types of extrusion, injection, calendering and compounding industries related to electrical wires, flooring materials, automobile interior materials, films, hoses, tubes and the like, general-purpose phthalate products such as diisononyl phthalate ( DINP), diisodecyl phthalate (DIDP) and the like.

However, since these phthalate products are substances whose use is regulated or needs to be regulated based on the purpose of the products, in order to meet market demand, general-purpose phthalate-free products such as terephthalate have been used. di(2-ethylhexyl) (DOTP or DEHTP) and the like, although an improvement in their quality is required.

In accordance with these environmental issues and demands for quality improvement to a level equal to or higher than that of existing products, there is a need to develop a new product capable of improving the quality of existing products while being environmentally friendly. atmosphere. To this end, there is ongoing research into the development of a new plasticizer composition that has superior physical properties to existing products and is environmentally friendly in order to ensure a vinyl chloride-based resin composition that is free of of environmental problems and has excellent quality.

[Description]

[Technical problem]

The present invention has been made in view of the above problems of the prior art, and relates to providing a plasticizer composition which, when used as a plasticizer for a resin composition, is capable of improving physical properties such as plasticization efficiency, loss of volatiles, light resistance, thermal stability, migration and the like at a higher level, and to a resin composition that includes the same.

[Technical solution]

One aspect of the present invention provides a plasticizer composition including: a cyclohexane-1,4-diester-based substance represented by the following Chemical Formula 1; an epoxidized alkyl ester composition including one or more compounds represented by the following Chemical Formula 2; and a citrate-based substance represented by the following Chemical Formula 3:

where in Chemical Formula 1 to Chemical Formula 3:

Ri and R ² are each independently a C8 alkyl group;

R ³ is a C ⁸ to C 20 alkyl group that includes one or more epoxy groups; and

R ⁴ to R ⁷ are each independently a C4 to C10 alkyl group,

where the sum of the number of carbon atoms of the alkyl group of R ⁴ and the average number of carbon atoms of the alkyl groups of R ⁵ to R ⁷ varies from 10 to 15.

Another aspect of the present invention provides a resin composition including: a resin in an amount of 100 parts by weight; and the plasticizer composition described above in an amount of 5 to 150 parts by weight.

[Advantageous effects]

A plasticizer composition according to an embodiment of the present invention is capable of improving physical properties such as plasticization efficiency, loss of volatiles, light fastness, heat resistance and the like to a higher level when used in a resin composition.

[Modes of invention]

Hereinafter the present invention will be described in more detail to promote understanding of the present invention.

As used in this invention, the term "alkyl group" may be understood as linear or branched without limitations other than a limitation on the number of carbons unless specifically mentioned otherwise.

In the present invention, an iodine value can be measured according to ASTM D5768-02.

In the present invention, the oxirane content can be measured according to ASTM D1652-04.

As used in this invention, the term "linear vinyl chloride polymer" is a type of vinyl chloride polymer, it can be polymerized through suspension polymerization, bulk polymerization or the like, and refers to a polymer that It is in the form of a porous particle in which a large number of pores with a size of several tens to several hundred micrometers are distributed and without cohesion and with excellent fluidity.

As used in this invention, the term "paste vinyl chloride polymer" is a type of vinyl chloride polymer that can be polymerized through microsuspension polymerization, microseeding polymerization, emulsion polymerization or the like, and refers to a polymer that is in the form of a fine, compact and non-porous particle with a size of several tens to several thousand nanometers and has cohesion and poor fluidity.

1. Plasticizer composition

A plasticizer composition according to an embodiment of the present invention includes: 1) a cyclohexane-1,4-diester-based substance represented by the following Chemical Formula 1; 2) an epoxidized alkyl ester composition including one or more compounds represented by the following Chemical Formula 2; and 3) a citrate-based substance represented by the following Chemical Formula 3:

where in Chemical Formula 1 to Chemical Formula 3:

R ¹ and R ² are each independently a C8 alkyl group;

R ³ is a C ⁸ to C 20 alkyl group that includes one or more epoxy groups; and

R ⁴ to R ⁷ are each independently a C4 to C10 alkyl group,

where the sum of the number of carbon atoms of the alkyl group of R ⁴ and the average number of carbon atoms of the alkyl groups from R ⁵ to R ⁷ varies from 10 to 15.

Hereinafter, each component of the plasticizer composition according to an embodiment of the present invention will be described in detail.

1) Substance based on cyclohexane-1,4-diester

The substance based on cyclohexane-1,4-diester is represented by Chemical Formula 1 and can impart environmental friendliness and excellent stability to the plasticizer composition. Furthermore, it can improve the processing properties, such as plasticizing efficiency, light fastness, absorption rate and the like, of the plasticizer composition.

Unless a diester group is attached to the 1 and 4 carbon positions of cyclohexane, plasticization efficiency, loss of volatiles, and the like are degraded.

When R ¹ and R ² in Chemical Formula 1 are alkyl groups having 9 or more carbon atoms, the plasticization efficiency, migration and the like are degraded, and when R ¹ and R ² are alkyl groups having 7 or less carbon atoms, the loss of volatiles is significantly degraded and therefore the amount of volatilized components is increased in processing with a resin, which can cause air pollution problems.

R ¹ and R ² in Chemical Formula 1 may each independently be any element selected from the group consisting of an n-octyl group, an isooctyl group and a 2-ethylhexyl group, and may be identical or different from each other.

The cyclohexane-1,4-diester-based substance may be dioctyl cyclohexane-1,4-dicarboxylate or di(2-ethylhexyl) cyclohexane-1,4-dicarboxylate.

The cyclohexane-1,4-diester-based substance may be included in an amount of 10 to 90% by weight, 20 to 90% by weight or 30 to 80% by weight with respect to the total weight of the plasticizer composition, the range of 30 to 80% by weight being preferred. When the condition described above is satisfied, a resin composition can be provided that is favorable in terms of plasticization efficiency, loss of volatiles, light fastness and mechanical properties such as tensile strength, elongation rate and the like.

When the cyclohexane-1,4-diester-based substance is prepared directly, a direct esterification or transesterification of cyclohexane-1,4-dicarboxylic acid or a derivative thereof with an alcohol can be carried out.

The cyclohexane-1,4-dicarboxylic acid derivative may be one or more selected from the group consisting of an anhydride of cyclohexane-1,4-dicarboxylic acid and an alkyl ester of cyclohexane-1,4-dicarboxylic acid. The alkyl ester may be a C1 to C6 alkyl ester.

The alcohol may be a C8 alkyl alcohol.

When the cyclohexane-1,4-diester-based substance represented by Chemical Formula 1 is prepared by direct esterification, the alcohol can be used in an amount of 2 to 10 moles, 2 to 8 moles, 2 to 6 moles or from 2 to 5 moles with respect to 1 mol of the cyclohexane-1,4-dicarboxylic acid or the derivative thereof, the range of 2 to 5 moles being preferred.

Direct esterification can be carried out in the presence of a catalyst, and the catalyst can be one or more selected from the group consisting of an inorganic acid, an organic acid and a Lewis acid.

The inorganic acid may be one or more selected from the group consisting of sulfuric acid, hydrochloric acid and phosphoric acid.

The organic acid may be one or more selected from the group consisting of p-toluenesulfonic acid, methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid and alkylsulfuric acid.

The Lewis acid may be one or more selected from the group consisting of aluminum derivatives (aluminum oxide, aluminum hydroxide), tin derivatives (C ³ to C ¹² fatty acid tin, tin oxide, tin hydroxide) , titanium derivatives (C ³ to Cs tetraalkyl titanate, titanium oxide, titanium hydroxide), lead derivatives (lead oxide, lead hydroxide) and zinc derivatives (zinc oxide, zinc hydroxide).

When the catalyst is a homogeneous catalyst, the catalyst can be used in an amount of 0.01 to 5 parts by weight or 0.01 to 3 parts by weight with respect to 100 parts by weight of the sum of cyclohexane-1 acid, 4-dicarboxylic acid or the derivative thereof and the alcohol, the range of 0.01 to 3 parts by weight being preferred.

When the catalyst is a heterogeneous catalyst, the catalyst can be used in an amount of 5 to 200 parts by weight or 5 to 100 parts by weight with respect to 100 parts by weight of the sum of cyclohexane-1,4-dicarboxylic acid or the derivative thereof and the alcohol, the range of 5 to 200 parts by weight being preferred.

Direct esterification can be carried out at 100 to 280 °C, 130 to 250 °C or 150 to 230 °C, with the range of 150 to 230 °C being preferred.

Direct esterification can be carried out for 3 to 30 hours or 3 to 25 hours, with the range of 3 to 25 hours being preferred.

Meanwhile, when the cyclohexane-1,4-diester-based substance represented by Chemical Formula 1 is prepared by transesterification, transesterification of a cyclohexane-1,4-dicarboxylic acid derivative with an alcohol can be carried out.

The cyclohexane-1,4-dicarboxylic acid derivative may be an alkyl ester of cyclohexane-1,4-dicarboxylic acid, and the methyl ester of cyclohexane-1,4-dicarboxylic acid is preferably used to facilitate the separation of a product of reaction.

The alcohol can be used in an amount of 2 to 10 moles, 2 to 8 moles, 2 to 6 moles, or 2 to 5 moles with respect to 1 mole of the cyclohexane-1,4-dicarboxylic acid derivative, with preference the range of 2 to 5 moles.

Transesterification can be carried out in the presence of a catalyst, which provides a reaction time reduction effect.

The catalyst may be one or more selected from the group consisting of a Lewis acid and an alkali metal.

The Lewis acid descriptions are the same as the description in direct esterification.

The alkali metal may be one or more selected from the group consisting of sodium alkoxide, potassium alkoxide, sodium hydroxide and potassium hydroxide.

The catalyst can be used in an amount of 0.01 to 5 parts by weight or 0.01 to 3 parts by weight with respect to 100 parts by weight of the sum of the cyclohexane-1,4-dicarboxylic acid derivative and the alcohol , the range of 0.01 to 3 parts by weight being preferred.

Transesterification can be carried out at 120 to 250 °C, 135 to 230 °C or 140 to 220 °C, with the range of 140 to 220 °C being preferred.

The transesterification can be carried out for 0.5 to 10 hours or 0.5 to 8 hours, with the range of 0.5 to 8 hours being preferred.

In order to promote the discharge of water or a lower alcohol such as methanol and the like that is produced by direct esterification or transesterification, one or more selected from the group consisting of benzene, toluene, xylene and cyclohexane may be additionally added. Furthermore, for the same purpose, commercially available nitrogen or the like in an entrained form can be used.

The cyclohexane-1,4-diester-based substance prepared by direct esterification or transesterification can be purified by performing a separate post-treatment. The subsequent treatment may be one or more selected from the group consisting of deactivation treatment (neutralization treatment, basic treatment) of the catalyst, washing treatment, distillation treatment (decompression or dehydration treatment) and adsorption purification treatment.

Unlike the preparation procedures described above, a preparation procedure can be used to prepare a cyclohexane-1,4-diester-based substance by hydrogenating a dialkyl terephthalate-based substance in the presence of a metal catalyst.

Hydrogenation is a reaction in which hydrogen is added in the presence of a metal catalyst to remove the aromaticity of a benzene ring from a terephthalate and may be a type of reduction reaction.

Hydrogenation is a reaction in which the terephthalate-based substance is reacted with hydrogen in the presence of a metal catalyst to synthesize a cyclohexane-1,4-diester-based substance represented by Chemical Formula 1, and the conditions of Hydrogenation may include all conventional hydrogenation conditions capable of hydrogenating only a benzene ring without affecting a substituted carbonyl group on benzene.

Hydrogenation can be carried out by including an additional organic solvent such as ethanol or the like, but the This invention is not limited thereto. The metal catalyst may be a Rh catalyst, a Pt catalyst, a Pd catalyst or the like, which is commonly used to hydrogenate a benzene ring, but the present invention is not limited thereto as long as it catalyzes a hydrogenation reaction. as described above.

2) Epoxidized alkyl ester composition

The epoxidized alkyl ester composition includes a compound represented by Chemical Formula 2. The epoxidized alkyl ester composition can impart environmental friendliness to the plasticizer composition and can improve the plasticization efficiency, light fastness and strength. heat.

When the epoxidized alkyl ester composition is applied to the plasticizer composition, an iodine value and an oxirane content thereof may be important factors. In particular, in the case of a plasticizing composition included in a food packaging material in which environmental friendliness is essential, an iodine value and an oxirane content may be critical for the plasticizing properties.

The iodine value indicates a content of double bonds present in a molecule, and the double bond content may be the content of double bonds remaining after epoxidation, such as the epoxidation of a vegetable oil or a fatty acid alkyl ester.

Furthermore, the oxirane content can vary depending on the number of epoxy groups contained in a substituent represented by R ³ .

That is, the iodine value and the oxirane content can be indicators of the degree to which epoxidation has occurred, so they can be related to each other to some extent and be theoretically inversely proportional to each other.

However, since the double bonds of a vegetable oil or fatty acid alkyl ester can vary substantially depending on a substance, the two parameters do not necessarily form an exact inverse or compensating relationship, and a substance having the value of Higher iodine may simultaneously have the highest oxirane content between two substances. Therefore, it may be preferable that a substance based on epoxidized fatty acid alkyl esters having an iodine value and an oxirane content be applied to a plasticizer composition used for an environmentally friendly food packaging material. within the ranges that will be described below.

The epoxidized alkyl ester composition may have an iodine value of less than 3.5 I ² g/100 g (hereinafter the set "I ² g/100 g" is omitted), 3.2 or less, or 3.0 or less, with 3.0 or less being preferable. When the condition described above is satisfied, a plasticizer composition can achieve a color suitable for use as a food wrapping material, and mechanical properties such as tensile strength, elongation rate and the like can also be improved.

The epoxidized alkyl ester composition may have an oxirane (C.O.) content equal to or greater than 3.5%, equal to or greater than 4.0%, equal to or greater than 4.2%, or equal to or greater than 4. 5%, preferably equal to or greater than 4.5%. When the condition described above is satisfied, the compatibility of a plasticizer composition with a resin is improved and therefore migration and processability can be improved, and mechanical properties such as tensile strength can also be improved. the elongation rate and the like.

The iodine value and oxirane content of the epoxidized alkyl ester composition can be used to predict the quality of a product, and an oxirane index (OI) can be used as an index thereof. Generally, an oxirane index may be 1.0 or more, 1.5 or more, or 2.0 or more, with 2.0 or more being preferred.

The "oxirane number" refers to a ratio between an oxirane content of the epoxidized fatty acid alkyl ester composition and an iodine value thereof, and may be a ratio between the epoxidized double bonds after epoxidation and the remaining unreacted double bonds.

The epoxidized alkyl ester composition may include one or more epoxidized fatty acid alkyl esters (eFAAEs), specifically, one or more compounds represented by Chemical Formula 2.

R ³ in Chemical Formula 2 can be represented by

where each of Li and L ² may be a C1 to C ¹⁰ alkylene group, R ¹⁰ may be a C1 to C 19 alkyl group, and n may vary from 0 to 5, where the sum of the number of carbon atoms in L ¹ , L ² and R ¹⁰ range from 8 to 20. Preferably, L ¹ is a C5 to C10 alkylene group, L ² is a C1 to C3 alkylene group, and R ¹⁰ is a C1 to C10 alkylene group.

R ⁴ in Chemical Formula 2 may be a C4 to C10 alkyl group or a C4 to C9 alkyl group, with a C4 to C9 alkyl group being preferred. When R ⁴ is an alkyl group having less than 4 carbon atoms, migration and loss of volatiles from a plasticizer composition may be considerably poor, and there may be air pollution problems caused by volatilization during processing, degradation of the tensile strength of a final product and the like. On the other hand, when R ⁴ is an alkyl group having more than 10 carbon atoms, the molecular weight is too high and therefore there may be a migration problem caused by the degradation of plasticization efficiency and compatibility with a resin.

R ⁴ may be one or more selected from the group consisting of a butyl group (abbreviated as B), an isobutyl group (abbreviated as iB), a pentyl group (abbreviated as P), an isopentyl group (abbreviated as iP), a hexyl group (abbreviated as Hx), an isohexyl group (abbreviated as iHx), a heptyl group (abbreviated as Hp), an isoheptyl group (abbreviated as iHp), an octyl group (abbreviated as nO), an isooctyl group (abbreviated as il)), a 2-ethylhexyl group (abbreviated as EH or O), a nonyl group (abbreviated as nN), an isononyl group (abbreviated as iN), a 6-methyloctyl group (abbreviated as MO), a decyl group (abbreviated as abbreviated as D), an isodecyl group (abbreviated as iD) and a 2-propylheptyl group (abbreviated as PH), with one or more groups selected from the group consisting of a butyl group, an isobutyl group, a 2-ethylhexyl group being preferred , an octyl group, an isononyl group and a 2-propylheptyl group.

In this case, specific examples of the isopentyl group include a 2-methylbutyl group, and specific examples of the isohexyl group include a 2-methylpentyl group, a 3-methylpentyl group, a 4-methylpentyl group, a 2,2-dimethylbutyl group, a 2,3-dimethylbutyl group, a 2-ethylbutyl group and the like.

The epoxidized alkyl ester composition may include one or more compounds represented by the following Chemical Formulas 2-1 to 2-18:

The epoxidized alkyl ester composition includes the epoxidized alkyl ester composition that includes one or more compounds represented by Chemical Formula 2, and may further include a saturated fatty acid alkyl ester composition that includes one or more compounds represented by the following chemical formula 4:

where in Chemical Formula 4:

R ₈ is a C8 to C20 alkyl group; and

R ₉ is a C4 to C10 alkyl group.

In the saturated fatty acid alkyl ester composition that includes one or more compounds represented by Chemical Formula 4, R ₈ may not include an epoxy group. In a process for preparing an alkyl ester of epoxidized fatty acid using an epoxidized oil and an alcohol, a fatty acid fraction of the epoxidized oil may be varied, there may be a fatty acid fraction that is not attached to an epoxy group, and the compound represented by Chemical Formula 4 may result of said fatty acid fraction.

However, when the content of the saturated fatty acid alkyl ester composition is about 80% by weight or more with respect to the total secondary plasticizer included in the epoxidized alkyl ester composition, the compatibility with a chloride resin vinyl can degrade. Therefore, when the content of the composition is 70% by weight or less, preferably 50% by weight or less, and more preferably 30% by weight or less, excellent compatibility with a chloride resin can be shown. vinyl.

In this case, the secondary plasticizer may refer to the epoxidized alkyl ester composition that includes one or more compounds represented by Chemical Formula 2 among the components of the plasticizer composition according to the present invention.

The epoxidized alkyl ester composition may further include one or more compounds represented by the following Chemical Formulas 4-1 to 4-12:

The epoxidized alkyl ester composition may be included in an amount of 5 to 70 % by weight, 5 to 60 % by weight or 10 to 50% by weight with respect to the total weight of the plasticizer composition, with the range of 10 being preferred. at 50% by weight. When the condition described above is satisfied, the plasticization efficiency, volatile loss and thermal stability can be improved.

The epoxidized alkyl ester composition can be prepared by direct esterification or transesterification of an epoxidized oil and a C4 to C10 alcohol.

The epoxidized oil may be a compound prepared by introducing a predetermined amount of epoxy groups through epoxidation of a vegetable oil, that is, one or more selected from the group consisting of epoxidized soybean oil, epoxidized castor oil, epoxidized linseed oil, epoxidized palm oil, an epoxidized stearate, an epoxidized oleate, epoxidized pine oil and an epoxidized linoleate.

The epoxidized oil may be, for example, one or more epoxidized oils represented by the following Chemical Formulas 5 to 11:

[Chemical formula 5]

Epoxidized oils represented by Chemical Formulas 5 to 11 include three ester groups and one or more epoxy groups in one molecule.

When the epoxidized oils represented by Chemical Formulas 5 to 11 and C4 to C10 alcohol are transesterified, the three ester groups can be separated into three ester compounds, and the separated ester compounds react with the alkyl group of the alcohol, thus forming an epoxidized alkyl ester composition. Transesterification can be carried out at a temperature of 40 to 230 °C, 50 to 200 °C, or 50 to 180 °C for 10 minutes to 10 hours, 30 minutes to 8 hours, or 1 to 6 hours.

Within the described temperature and time ranges, a desired substance based on epoxidized alkyl ester can be effectively obtained. In this case, the reaction time can be calculated from the moment at which the reaction temperature is reached after raising the temperature of the reactants.

Transesterification can be carried out in the presence of a basic catalyst, acidic catalyst or metal catalyst, which provides a reaction time reduction effect.

Examples of the acid catalyst include sulfuric acid, methanesulfonic acid, p-toluenesulfonic acid, and the like, and examples of the metal catalyst include an alkoxide-based organometallic catalyst, a metal oxide catalyst, a metal salt catalyst, and a metal in yes, they include sodium, potassium, or similar.

A metallic component of the metallic catalyst may be, for example, any one or a mixture of two or more metals selected from the group consisting of sodium, potassium, tin, titanium and zirconium.

Furthermore, a process for removing, after transesterification, a polyhydric alcohol produced and the reaction by-products, as well as an unreacted alcohol, can be carried out by separation, washing and distillation.

In the purification process, specifically, the products, unreacted alcohol and the like can be cooled and maintained at 80 to 100 °C for a predetermined time after transesterification. In this case, layer separation occurs and this can result in an upper layer containing an epoxidized alkyl ester and an alcohol and a lower layer containing glycerin and other byproducts. Next, to neutralize a catalyst, an aqueous solution can be added to neutralize a catalyst to induce neutralization and washing.

Neutralization and washing procedures can be performed after first separating a bottom layer containing most of the byproducts. In the neutralization and washing procedures, the byproducts included in the lower layer can be dissolved in water and discharged. Washing can then be performed repeatedly to recover and remove unreacted alcohol and moisture.

However, it may be necessary to vary the neutralization and washing procedures depending on the number of carbon atoms of an alcohol used in the transesterification.

For example, in the case of using butanol having 4 carbon atoms, when the neutralization and washing procedures are carried out directly, wastewater may be produced and therefore it may be preferable to previously remove the butanol by distillation. However, in this case, since the catalyst remains active, glycerol as a by-product and an epoxidized alkyl ester as a product can react inversely to produce an epoxidized oily substance, such as a diglyceride, a triglyceride or the like. Therefore, it is necessary to design the procedure with caution.

As another example, in the case of using 2-ethylhexyl alcohol having 8 carbon atoms, no wastewater is produced due to the low solubility of 2-ethylhexyl alcohol in water. Therefore, both cases where an alcohol is removed after neutralization and washing procedures and where neutralization and washing procedures are performed after removing byproducts from a lower layer can proceed without critical problems.

3) Citrate-based substance

The citrate-based substance is represented by Chemical Formula 3 and can improve the absorption rate, plasticization efficiency, migration resistance and the like of the plasticizer composition.

When a citrate-based substance that includes an acetyl group instead of a hydroxyl group is used in Chemical Formula 3, the physical properties (e.g., plasticization efficiency) of a plasticizer composition may be degraded. Furthermore, procedures, time and installation costs may be additionally required for the removal of residual acetic acid generated as a by-product during the preparation of a citrate-based substance, leading to increased manufacturing costs.

Therefore, a citrate-based substance that includes an acetyl group instead of a hydroxyl group in Chemical Formula 3 exhibits degraded plasticization efficiency compared to the citrate-based substance represented by Chemical Formula 3, and it is necessary increasing an additional amount of the citrate-based substance to overcome the degraded plasticization efficiency and therefore the price of a product can be increased. Therefore, considering various aspects such as marketability, economic viability, physical properties and the like, a citrate-based substance including an acetyl group is not preferred.

R ⁵ to R ⁷ in Chemical Formula 3 are each independently a C4 to C10 alkyl group, preferably, a C4 to C8 alkyl group or a C5 to C10 alkyl group.

When the condition described above is satisfied, the citrate-based substance has an appropriate molecular weight, and therefore, the plasticization efficiency and absorption rate of the plasticizer composition can be improved.

When R ⁵ to R ⁷ are each independently alkyl groups having less than 4 carbon atoms, the tensile strength and loss of volatiles of the plasticizer composition are degraded, thereby resulting in degradation of the quality of a final product and a relative increase in an amount of the composition volatilized during processing, which increases the possibility of adverse effects on the atmosphere. Furthermore, to overcome these problems, it is necessary to add excess plasticizer composition in an amount equal to the amount volatilized and is therefore economically disadvantageous.

When R ⁵ to R ⁷ are each independently alkyl groups having more than 10 carbon atoms, the molecular weight of the citrate-based substance increases and therefore the plasticization efficiency and absorption rate of the plasticizer composition degrade quite a bit.

Meanwhile, in the calendering industry which requires, as key quality factors, plasticizing efficiency, an absorption and migration rate, R ⁵ to R ⁷ are preferably a C4 to C8 alkyl group, more preferably a C4 to C6 alkyl group . Furthermore, in the composites industry that requires, as key quality factors, tensile strength and tensile retention, an elongation rate and elongation retention, loss of volatiles and the like, R ⁵ to R ⁷ are preferably an alkyl group C5 to C10, more preferably a C8 to C10 alkyl group.

R ⁵ to R ⁷ are each independently one or more selected from the group consisting of an n-butyl group, an isobutyl group, an n-pentyl group, an isopentyl group, an n-hexyl group, an isohexyl group, a n-heptyl, an isoheptyl group, an n-octyl group, an isooctyl group, a 2-ethylhexyl group, an n-nonyl group, an isononyl group, a 2-propylheptyl group and an isodecyl group, with one or more selected being preferred of the group consisting of an n-butyl group, an isobutyl group, an n-pentyl group, an isopentyl group, a 2-ethylhexyl group and an isononyl group.

Two of R ⁵ to R ⁷ can be the same, and the remaining one can be different. In this case, the citrate-based substance represented by Chemical Formula 3 may be a citrate group having combined substituents selected from an n-butyl group, an isobutyl group, an n-pentyl group, an isopentyl group, a 2-group -ethylhexyl and an isononyl group.

Alternatively, R ⁵ to R ⁷ may be equal. In this case, the citrate-based substance represented by Chemical Formula 3 may be one or more selected from the group consisting of tri-n-butyl citrate (TnBC), triisobutyl citrate (TiBC), tri-n citrate -pentyl (TnPC), triisopentyl citrate (TIPC), trihexyl citrate (THxC), triheptyl citrate (THpC), triisoheptyl citrate (TIHpC), tri(2-ethylhexyl) citrate (TEHC), triisononyl citrate ( TINC) and triisodecyl citrate (TIDC).

The citrate-based substance can be included in an amount of 5 to 70% by weight, 5 to 60% by weight or 10 to 50% by weight with respect to the total weight of the plasticizer composition, the range of 10 to 50% being preferred. 50% by weight.

When the condition described above is satisfied, the quality such as plasticization efficiency, absorption rate, migration resistance and the like can be improved.

When the citrate-based substance represented by Chemical Formula 3 is prepared directly, direct esterification or transesterification of citric acid or a derivative thereof with an alcohol can be carried out.

The citric acid derivative may be one or more selected from the group consisting of a citric acid anhydride and an alkyl ester of citric acid. The alkyl ester may be a C1 to C6 alkyl ester.

The alcohol may be a C4 to C10 alcohol, preferably a C4 to C8 alcohol or a C5 to C10 alcohol.

When the citrate-based substance represented by Chemical Formula 3 is prepared by direct esterification or transesterification, the alcohol can be used in an amount of 3 to 15 moles, 3 to 12 moles or 3 to 10 moles with respect to 1 mol of citric acid or the derivative thereof, the range of 3 to 10 moles being preferred.

Additional descriptions of direct esterification and transesterification are the same as the descriptions in the preparation procedure of the cyclohexane-1,4-diester-based substance represented by Chemical Formula 1.

Meanwhile, the sum of the number of carbon atoms of the alkyl group of R ⁴ and the average number of carbon atoms of the alkyl groups of Rs to R ⁷ is in the range of 10 to 15. When the range described above is satisfied , excellent plasticizing efficiency is presented, and migration loss, volatile loss, tensile strength, absorption rate and heat resistance can also be improved. However, below the range described above, migration loss, tensile strength and elongation rate can degrade significantly. Furthermore, above the range described above, migration loss, tensile strength, elongation rate and absorption rate can be significantly degraded.

2. Resin composition

A resin composition according to another embodiment of the present invention includes: a resin in an amount of 100 parts by weight; and the plasticizer composition according to an embodiment of the present invention in an amount of 5 to 150 parts by weight.

The resin may be any resin known in the art. For example, a mixture of one or more elements selected from the group consisting of a linear vinyl chloride polymer, a vinyl chloride polymer, paste vinyl, an ethylene-vinyl acetate copolymer, an ethylene polymer, a propylene polymer, polyketone, polystyrene, polyurethane, natural rubber, synthetic rubber and a thermoplastic elastomer, but the present invention is not limited thereto.

The plasticizer composition may be included in an amount of 5 to 150 parts by weight, preferably 5 to 130 parts by weight or 10 to 120 parts by weight with respect to 100 parts by weight of the resin.

Generally, a resin in which a plasticizer composition is used can be subjected to melt processing or plastisol processing to prepare a resin product, and the melt processing resin and the plastisol processing resin can be produced in a manner different depending on a polymerization procedure.

For example, when used in melt processing, a vinyl chloride polymer is prepared by suspension polymerization or the like and is therefore used as a solid phase resin particle having a large average particle diameter. . In this case, the vinyl chloride polymer is called linear vinyl chloride polymer. When used in plastisol processing, a vinyl chloride polymer is prepared through emulsion polymerization or the like and is therefore used as a fine solphasic resin particle. In this case, the vinyl chloride polymer is called paste vinyl chloride polymer.

In the case of the linear vinyl chloride polymer, the plasticizer composition is preferably included in an amount of 5 to 80 parts by weight with respect to 100 parts by weight of the polymer, and in the case of the paste vinyl chloride polymer, The plasticizer composition is preferably included in an amount of 40 to 120 parts by weight with respect to 100 parts by weight of the polymer.

The resin composition may further include a filler. The filler may be included in an amount of 0 to 300 parts by weight, preferably 50 to 200 parts by weight, and more preferably 100 to 200 parts by weight with respect to 100 parts by weight of the resin.

The load may be any load known in the art without particular limitation. For example, a mixture of at least one or more selected from silica, magnesium carbonate, calcium carbonate, hard carbon, talc, magnesium hydroxide, titanium dioxide, magnesium oxide, calcium hydroxide, aluminum hydroxide, aluminum silicate, magnesium silicate and barium sulfate.

Furthermore, the resin composition may additionally include other additives such as a stabilizer, and the like, as necessary. Additives such as a stabilizer and the like may be included, for example, in an amount of 0 to 20 parts by weight, preferably 1 to 15 parts by weight with respect to 100 parts by weight of the resin.

Examples of the stabilizer include a calcium-zinc (Ca-Zn) based stabilizer such as a calcium-zinc complex stearate and the like or a barium-zinc (Ba-Zn) based stabilizer, but the present invention is not limited particularly these.

The resin composition can be applied to both melt processing and plastisol processing as described above, where the melt processing can be, for example, calendering processing, extrusion processing or injection processing, and plastisol processing It may be coating processing or the like.

Hereinafter, the present invention will be described in detail with reference to embodiments so that those skilled in the art can easily carry out the present invention.

Preparation example 1

516.5 g of cyclohexane-1,4-dicarboxylic acid, 1170 g of 2-ethylhexanol and 1.55 g of tetraisopropyl titanate as catalyst were placed in a 3 L four-neck reaction vessel equipped with a cooler, a condenser, a decanter, a reflux pump, a temperature controller, a stirrer and the like, and then the temperature of the reaction vessel was adjusted to 230 °C. Then, esterification was carried out for about 6 hours while continuously introducing nitrogen gas and was terminated when an acid value reached 0.1.

Once the reaction was complete, distillation extraction was performed under reduced pressure to remove unreacted raw materials. Then, neutralization, dehydration, and filtration procedures were performed to prepare 1,154 g of di(2-ethylhexyl) cyclohexane-1,4-dicarboxylate (1,4-DEHCH) (yield: 97%).

Preparation example 2: eFABE preparation

1,000 g of epoxidized soybean oil (ESO) with an oxirane content of 6.97% and an iodine value of 1.93 (I ² g/100 g), 500 g of butanol and 5.5 g of tetra(n-butyl) titanate as a catalyst in a reaction vessel of 3 L four-necks equipped with a cooler, a condenser, a decanter, a reflux pump, a temperature controller, a stirrer and the like, and the temperature of the reaction vessel was gradually raised to about 180 ° C.

After the ESO feedstock was confirmed to have been completely reacted and consumed through gas chromatography analysis, the reaction was terminated. Subsequently, glycerin as a by-product and unreacted raw materials were removed, and the product was purified, finally obtaining 1,160 g of an epoxidized fatty acid butyl ester (eFABE) composition with an oxirane content of 5. 18% and an iodine value of 1.68 g and that includes compounds represented by the following Chemical Formulas 2-1,2-2, 2-3, 4-1, and 4-2.

Preparation Example 3: eFAPE Preparation

1,180 g of an epoxidized fatty acid pentyl ester (eFAPE) composition were prepared in the same manner as in Preparation Example 2, except that 500 g of 1-pentanol was used instead of butanol. In this case, the eFAPE had an oxirane content of 5.51% and an iodine value of 1.40 and included compounds represented by the following Chemical formulas 2-4, 2-5, 2-6, 4-1 and 4-2.

Preparation example 4: Preparation of eFAHxE

1,180 g of an epoxidized fatty acid hexyl ester (eFAHxE) composition were prepared in the same manner as in Preparation Example 2, except that 500 g of 1-hexanol was used instead of butanol. In this case, an epoxidized fatty acid pentyl ester composition had an oxirane content of 5.51% and an iodine value of 1.40 and included compounds represented by the following Chemical Formulas 2-7, 2-8, 2 -9, 4-5 and 4-6.

Preparation example 5: Preparation of eFAEHE

1,180 g of an epoxidized fatty acid ethylhexyl ester (eFAEHE) composition were obtained with an oxirane content of 5.21% and an iodine value of 1.70 and which included the compounds represented by the following Chemical Formulas 2-10 , 2-11, 2-12, 4-7 and 4-8 in the same manner as in Preparation Example 2, except that 500 g of 2-ethylhexanol was used instead of butanol.

Preparation example 6: Preparation of eFAINE

1,250 g of an epoxidized fatty acid isononyl ester (eFAINE) composition with an oxirane content of 5.22% and an iodine value of 1.72 and including the compounds represented by the following Chemical formulas 2-13 were obtained. , 2-14, 2-15, 4-9 and 4-10 in the same manner as in Preparation Example 2, except that 600 g of isononanol was used instead of butanol.

Preparation example 7: Preparation of eFAPHE

1,280 g of an epoxidized fatty acid propylheptyl ester (eFAPHE) composition with an oxirane content of 5.00% and an iodine value of 1.47 and including the compounds represented by the following Chemical Formulas 2-16 were obtained. , 2-17, 2-18, 4-11 and 4-12 in the same manner as in Preparation Example 2, except that 600 g of 2-propylheptanol was used instead of butanol.

The substances according to the Preparation Examples were mixed in contents as described in [Table 1] to [Table 5] below and stirred, thus preparing plasticizing compositions. The physical properties of the plasticizer compositions were evaluated according to the following test elements.

<Test elements>

Hardness measurement (Shore "A" and Shore "D")

According to ASTM D2240, the hardness of a 3 mm thick sample was measured for 10 seconds.

Migration loss measurement (%)

According to KSM-3156, glass plates were attached to both sides of a 1 mm thick sample, and then a load of 1 kgf/cm2 was applied to it. The sample was put in a hot air convection oven (80 °C) for 72 hours, then removed from the oven and cooled to room temperature. Then, the glass plates attached to both sides of the sample were removed, the weights of the sample were measured before being placed inside and after being removed from the oven, and the resulting weights were substituted into the following Equation 1 to obtain a value of loss due to migration.

<Equation 1>

Migration loss (%) = [(Initial weight of the sample before being placed in the oven) -(Weight of the sample after being removed from the oven)] / (Initial weight of the sample before being placed in the oven ) * 100

Measurement of volatile loss (%)

A 1 mm thick sample was exposed to 80 °C for 72 hours, then its weight was measured and the resulting weight was substituted into the following Equation 2 to obtain a volatile loss value.

<Equation 2>

Volatile loss (%) = [(Initial weight of the sample) -(Weight of the sample after being exposed)] / (Initial weight of the sample before being placed in the oven) * 100

Tensile strength measurement (kgf/cm2)

In accordance with ASTM D638, a 1 mm thick sample was removed at a feed rate of 200 mm/min using a universal testing machine (UTM; 4466 manufactured by Instron), and then a time point was determined at the that the sample broke.

Measurement of elongation rate (%)

In accordance with ASTM D638, a 1 mm thick sample was removed at a feed rate of 200 mm/min using a universal testing machine (UTM; 4466 manufactured by Instron), and then a time point was determined at the that the sample broke. A length at the time point was then substituted into the following Equation 3 to calculate an elongation rate.

<Equation 3>

Elongation rate (%) = [(Length at the time point when the sample broke) / (Initial length)] * 100

Absorption rate

The absorption rate was evaluated by measuring the time required to stabilize the torque of a mixer in which a resin and a composition are mixed using a planetary mixer (Brabender, P600) at 77 ° C and 60 rpm.

Heat resistance

Heat resistance was observed by operating a 0.5 T thick sample at a speed of 25 mm/3 min using a Mathis oven at 220 °C and was evaluated using 5 scales (1 (excellent) to 5 (poor)). .

Experimental example: Evaluation of physical properties

The samples were prepared using plasticizer compositions of the Examples and Comparative Examples described in [Table 1] to [Table 5] below.

For sample preparation, according to ASTM D638, 100 parts by weight of polyvinyl chloride (LS100 manufactured by LG Chem Ltd.), 40 parts by weight of each of the plasticizer compositions prepared in Examples and Comparative Examples were mixed. , and 3 parts by weight of a stabilizer (BZ153T manufactured by SONGWON) while stirring at 98 ° C and 700 rpm, and the resulting mixture was subjected to roller grinding at 160 ° C for 4 minutes and pressed with a press at 180 °C for 3 minutes (low pressure) and for 2.5 minutes (high pressure), thus preparing 1 mm thick and 3 mm thick samples.

The samples were subjected to tests to evaluate the physical properties described above, and the results thereof are shown in the following [Table 1] to [Table 5]. Examples 1 and 10 are Reference Examples.

T l 1

continuation

Tl 21

T l 1

Tl 41

T l 1

1.4- DBCH: Dibutyl cyclohexane-1,4-dicarboxylate (LG Chem Ltd.)

1.4- DIDCH: Diisodecyl cyclohexane-1,4-dicarboxylate (LG Chem Ltd.)

TBC: Tributyl Citrate (LG Chem Ltd.)

TPC: Tripentyl Citrate (LG Chem Ltd.)

THxC: Trihexyl citrate (LG Chem Ltd.)

TEHC: Tris(2-ethylhexyl) citrate (LG Chem Ltd.)

TINC: Triisononyl citrate (LG Chem Ltd.)

TPHC: Tris(2-propylheptyl) citrate (LG Chem Ltd.)

ATBC: Acetyl tributyl citrate (LG Chem Ltd.)

Referring to [Table 1] to [Table 5], it can be seen that Example 1 to Example 15 are excellent in terms of plasticization efficiency, migration loss, volatile loss, tensile strength, elongation rate, absorption rate and heat resistance. Furthermore, with reference to Examples 1 to 10, it can be seen that Examples 2 to 9, in which the sum of the number of carbon atoms of R ⁴ and the average number of carbon atoms of R ⁵ , R6, and R ⁷ varies from 10 to 15, they are significantly excellent in terms of migration loss, volatile loss, tensile strength and elongation rate compared to Example 1 and Example 10. Additionally, with reference to Examples 1 to 4, it can be seen that as the number of carbon atoms of R ⁴ of the epoxidized alkyl ester composition increases, the migration loss, volatile loss, tensile strength and the elongation rate. Furthermore, with reference to Examples 6 to 9, it can be seen that as the average number of carbon atoms from R ⁵ to R ⁷ decreases, the plasticization efficiency, the loss of volatiles, the elongation rate and the rate absorption are excellent. However, Examples 4 and 5 show different aspects from Examples 6 to 9, which were attributed to the characteristics of tributyl citrate. Furthermore, with reference to Examples 11 to 14, it can be seen that as the content of the cyclohexane-1,4-diester-based substance decreases, the migration loss, the loss of volatiles, the elongation rate and the absorption rate.

On the other hand, it can be seen that Comparative Example 1 which includes only a substance based on cidohexane-1,4-diester presented a significantly low heat resistance compared to the Examples, Comparative Example 2 which did not include a substance citrate base exhibited significantly low tensile strength compared to the Examples, Comparative Example 3 which did not include an epoxidized alkyl ester composition exhibited significantly low heat resistance compared to the Examples, Comparative Example 4 which included Dibutyl cyclohexane-1,4-dicarboxylate presented significantly degraded properties in terms of migration loss and loss of volatiles compared to the Examples, Comparative Example 5 that included diisodecyl cyclohexane-1,4-dicarboxylate presented significantly degraded properties in terms of of plasticization efficiency and an absorption rate compared to the Examples, Comparative Example 6 that did not include a substance based on cyclohexane-1,4-diester presented significantly degraded properties in terms of migration loss, loss of volatiles, resistance tensile strength, elongation rate and heat resistance compared to the Examples, Comparative Example 7 which included dibutyl cyclohexane-1,4-dicarboxylate and which did not include a citrate-based substance exhibited degraded properties in terms of loss by migration, loss of volatiles, tensile strength and an elongation rate compared to the Examples, Comparative Example 8 that included diisodecyl cyclohexane-1,4-dicarboxylate and that did not include a citrate-based substance presented an efficiency of degraded plasticization and a significantly low elongation rate and a significantly low absorption rate compared to the Examples, and Comparative Example 9 that included acetyl tributyl citrate exhibited low heat resistance compared to the Examples.

Claims (12)

1. A plasticizer composition comprising: a substance based on cidohexane-1,4-diester represented by the following Chemical Formula 1; an epoxidized alkyl ester composition comprising one or more compounds represented by the following Chemical Formula 2; and a citrate-based substance represented by the following Chemical Formula 3:

In Chemical Formula 1 to Chemical Formula 3, where: R1 to R2 are each independently a C8 alkyl group, R3 is a C8 to C20 alkyl group comprising one or more epoxy groups, and R ⁴ to R ⁷ are each independently a C4 to C10 alkyl group, where the sum of the number of carbon atoms of the alkyl group of R4 and the average number of carbon atoms of the alkyl groups of R5 to R ₇ varies from 10 to 15. 2. The plasticizer composition of claim 1, wherein R ¹ and R ² are each independently any element selected from the group consisting of an n-octyl group, an isooctyl group and a 2-ethylhexyl group. 3. The plasticizer composition of claim 1, wherein the epoxidized alkyl ester composition has an iodine value of less than 3.5 b g/100 g. 4. The plasticizer composition of claim 1, wherein the epoxidized alkyl ester composition has an oxirane (CO) content equal to or greater than 3.5%. 5. The plasticizer composition of claim 1, wherein R ⁴ is selected from the group consisting of a butyl group, an isobutyl group, a pentyl group, an isopentyl group, a hexyl group, an isohexyl group, a 2-ethylhexyl group , an octyl group, an isononyl group, a decyl group, an isodecyl group and a 2-propylheptyl group. 6. The plasticizer composition of claim 1, wherein R ⁵ to R ⁷ are each independently a C4 to C8 alkyl group. 7. The plasticizer composition of claim 1, wherein R ⁵ to R ⁷ are each independently a C5 to C10 alkyl group. 8. The plasticizer composition of claim 1, wherein R ⁵ to R ⁷ are each independently any element selected from the group consisting of an n-butyl group, an isobutyl group, an npentyl group, an isopentyl group, a n-hexyl, an isohexyl group, an n-heptyl group, an isoheptyl group, a noctyl group, an isooctyl group, a 2-ethylhexyl group, an n-nonyl group, an isononyl group, a 2-propylheptyl group and a isodecyl. 9. The plasticizer composition of claim 1, which includes, with respect to a total weight thereof, from 10 to 90% by weight of the substance based on cyclohexane-1,4-diester, from 5 to 70% by weight of the epoxidized alkyl ester composition, and from 5 to 70% by weight of the citrate-based substance. 10. The plasticizer composition of claim 1, wherein the epoxidized alkyl ester composition comprises the epoxidized alkyl ester composition comprising one or more compounds represented by Chemical Formula 2, and further includes an acid alkyl ester composition saturated fat that includes one or more compounds represented by the following Chemical Formula 4:

In the chemical formula 4 where Rs is a C8 to C20 alkyl group, and R ⁹ is a C4 to C10 alkyl group. 11. A resin composition comprising: a resin in 100 parts by weight; and the plasticizing composition of claim 1 in 5 at a rate of 150 parts by weight. 12. The resin composition of claim 11, wherein the resin is one or more elements selected from the group consisting of a linear vinyl chloride polymer, a paste vinyl chloride polymer, an ethylene-vinyl acetate copolymer , an ethylene polymer, a propylene polymer, polyketone, polystyrene, polyurethane, natural rubber, synthetic rubber and a thermoplastic elastomer.