Triglyceride-based plasticizer composition and resin composition containing the same

Abstract

The present invention relates to a triester-based plasticizer composition, characterized by comprising the product of the esterification of a carboxylic acid composition comprising a mixture of hexanoic acid isomers and benzoic acid with a triol. If this plasticizer composition is applied to a resin, compared with the case of using a conventional plasticizer, the migration resistance and volatile loss can be maintained at the same level, and the mechanical properties, absorption rate, stress migration and plasticization efficiency can be significantly improved.

Description

TECHNICAL FIELD

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims the benefit of priority based on Korean Patent Application No. 10-2021-0080756, filed on Jun. 22, 2021, the entire contents of which are incorporated herein by reference. TECHNICAL FIELD

[0004] The present invention relates to a plasticizer composition containing one or more triester groups, and a resin composition containing the same. BACKGROUND ART

[0005] Generally, plasticizers are obtained by reacting alcohols with polycarboxylic acids such as phthalic acid and adipic acid to form corresponding esters. In addition, in consideration of internal and external regulations on phthalate plasticizers harmful to the human body, continuous research is being conducted on plasticizer compositions that can replace phthalate plasticizers, such as terephthalate esters, adipate esters, and other polymeric plasticizers.

[0006] Meanwhile, regardless of the industrial type, including plastic sol industrial types such as floor materials, wallpapers, and hard and soft sheets, calendering industrial types, or extrusion / injection compounding industrial types, the demand for eco-friendly products is increasing. In order to enhance the quality performance, processability, and productivity of the finished product, considering discoloration, migration, mechanical properties, etc., a suitable plasticizer is required.

[0007] According to the properties required by the industrial type in each application field, such as tensile strength, elongation, light resistance, migration, gelling properties, and absorption rate, auxiliary materials such as plasticizers, fillers, stabilizers, viscosity reducers, dispersants, defoamers, and foaming agents are mixed with PVC resin.

[0008] For example, in the case of applying bis(2-ethylhexyl) terephthalate (DEHTP) (which is relatively inexpensive and widely used in plasticizer compositions applicable to PVC), the hardness or sol viscosity is high, the absorption rate of the plasticizer is relatively slow, and migration and stress migration are poor.

[0009] As an improvement to the above limitations, as a composition including DEHTP, an ester exchange product with butanol can be considered as a plasticizer. However, although the plasticizing efficiency is improved, the volatilization loss or thermal stability is poor, the mechanical properties are somewhat reduced, and the physical properties need to be improved. Therefore, generally speaking, except for the method of compensating for the defects by mixing with different second plasticizers, there is currently no solution.

[0010] However, in the case of using a second plasticizer, there are drawbacks of generating the following undesirable defects: the change in physical properties is difficult to predict; the application may be a factor in increasing the unit cost of the product; except for specific cases, the improvement in physical properties is not clearly shown; and problems related to resin compatibility may occur.

[0011] In addition, if, as a trimellitate product, materials such as tris(2-ethylhexyl) trimellitate or trisisononyl trimellitate are used to improve the poor migration and loss properties of DEHTP products, the migration or loss properties can be improved, but the plasticizing efficiency may decrease, and a large amount of this material needs to be injected to provide a resin with a suitable plasticizing effect. Considering the relatively high unit price of this product, its commercialization is impossible.

[0012] Therefore, there is a need to develop products for solving the environmental problems of conventional phthalate products or products for improving the poor physical properties of environmentally friendly products (which are used to improve the environmental problems of the phthalate products). Summary of the Invention

[0013] Technical Problem

[0014] The present invention provides a plasticizer composition which can maintain the same level of migration resistance and volatile loss as when using a conventional plasticizer, while significantly improving mechanical properties, absorption rate, stress migration, and plasticizing efficiency by containing a triester which is a product of the esterification reaction of a carboxylic acid composition containing a mixture of hexanoic acid isomers and benzoic acid with a trihydric alcohol.

[0015] Technical Solution

[0016] To solve this problem, the present invention provides a plasticizer composition and a resin composition.

[0017] (1) The present invention provides a triester-based plasticizer composition containing one or more triesters of the following formula 1, wherein R1 to R3 in formula 1 are from a carboxylic acid composition containing a mixture of hexanoic acid isomers and benzoic acid:

[0018] [Formula 1]

[0019]

[0020] In formula 1,

[0021] R1 to R3 are each independently a n-pentyl group, a branched pentyl group, a cyclopentyl group, or a phenyl group, and

[0022] R4 and R5 are each independently hydrogen or an alkyl group having 1 to 4 carbon atoms.

[0023] (2) The present invention provides a plasticizer composition according to (1), wherein the carboxylic acid composition comprises a mixture of hexanoic acid isomers and benzoic acid in a weight ratio of 99:1 to 50:50.

[0024] (3) The present invention provides a plasticizer composition according to (1) or (2), wherein the mixture of hexanoic acid isomers has a degree of branching of 2.0 or less.

[0025] (4) The present invention provides a plasticizer composition according to any one of (1) to (3), wherein the mixture of hexanoic acid isomers comprises 2-methylvaleric acid and 3-methylvaleric acid.

[0026] (5) The present invention provides a plasticizer composition according to any one of (1) to (4), wherein the mixture of hexanoic acid isomers comprises n-hexanoic acid, 2-methylvaleric acid, 3-methylvaleric acid, and cyclopentanecarboxylic acid.

[0027] (6) The present invention provides a plasticizer composition according to any one of (1) to (5), wherein, relative to a total of 100 parts by weight of the mixture, the mixture of hexanoic acid isomers comprises 20 to 95 parts by weight of branched-chain hexanoic acid.

[0028] (7) The present invention provides a plasticizer composition according to any one of (1) to (6), wherein, relative to a total of 100 parts by weight of the mixture, the mixture of hexanoic acid isomers comprises 30 parts by weight or less of cyclopentanecarboxylic acid.

[0029] (8) The present invention provides a plasticizer composition according to any one of (1) to (7), wherein R4 and R5 are hydrogen.

[0030] (9) The present invention provides a resin composition comprising: 100 parts by weight of a resin; and 5 to 150 parts by weight of the plasticizer composition according to claim 1.

[0031] (10) The present invention provides a resin composition according to (9), wherein the resin is one or more selected from linear vinyl chloride polymers, paste vinyl chloride polymers, ethylene-vinyl acetate copolymers, ethylene polymers, propylene polymers, polyketones, polystyrenes, polyurethanes, natural rubbers, and synthetic rubbers.

[0032] Advantageous Effects

[0033] The plasticizer composition according to an embodiment of the present invention, when used in a resin composition, can maintain the same level of migration resistance and volatile loss as conventional plasticizers, and can significantly improve mechanical properties, absorption rate, stress migration, and plasticization efficiency. Detailed Embodiments

[0034] It is to be understood that the terms or words used in this disclosure and the claims should not be construed as having the meaning defined in the ordinary or dictionary sense, but rather should be interpreted based on the concept that the inventor can appropriately define the terms so as to best explain the principles of the present invention and in accordance with the technical scope of the present invention.

[0035] Definition of terms

[0036] The term "composition" as used in this disclosure includes a mixture of materials containing the corresponding composition, as well as reaction products and decomposition products formed from the materials of the corresponding composition.

[0037] The term "isomer" as used in this disclosure is not intended to distinguish all meanings of isomers, but rather is intended to refer to structural isomers, that is, the relationship having the same number of carbons but different bonding structures, in order to distinguish these types, and is not intended to refer to materials that are distinguished as stereoisomers such as enantiomers and diastereomers.

[0038] The term "linear vinyl chloride polymer" as used in this disclosure can be a type of vinyl chloride polymer, and is polymerized by suspension polymerization, bulk polymerization, etc., and can refer to a polymer having a porous particle shape (in which a large number of pores with sizes of dozens to hundreds of micrometers are dispersed), having no adhesiveness, and having excellent fluidity.

[0039] The term "paste vinyl chloride polymer" as used in this disclosure can be a type of vinyl chloride polymer, and is polymerized by miniemulsion polymerization, microseed polymerization, emulsion polymerization, etc., and can refer to a polymer having fine particles without pores and with sizes of dozens to thousands of nanometers, having adhesiveness and poor fluidity.

[0040] The terms "comprising" and "having" and their derivatives in the present invention - although these terms are specifically disclosed or not specifically disclosed - are not intended to exclude the presence of optional additional components, steps or methods. To avoid any uncertainty, unless otherwise stated to the contrary, all compositions claimed by using the term "comprising" may include optional additional additives, auxiliaries or compounds, including polymers or any other materials. In contrast, the term "consisting essentially of" excludes unnecessary operations and excludes optional other components, steps or methods from the scope of the optional successive description. The term "consisting of" excludes optional components, steps or methods that are not specifically described or stated.

[0041] Measurement method

[0042] In the present disclosure, the content analysis of the components in the composition is carried out by gas chromatography measurement using a gas chromatography device of Agilent Co. (product name: Agilent 7890GC, column: HP-5, carrier gas: helium (flow rate 2.4 ml / min), detector: F.I.D., injection volume: 1 μl, initial value: 70 °C / 4.2 minutes, final value: 280 °C / 7.8 minutes, program rate: 15 °C / minute).

[0043] In the present disclosure, "hardness" refers to the Shore hardness (Shore "A" and / or Shore "D") at 25 °C, and is measured under the conditions of 3T 10s according to ASTM D2240. This hardness can be an index for evaluating the plasticizing efficiency, and the lower the value, the better the plasticizing efficiency.

[0044] In the present disclosure, according to the ASTM D638 method, the test equipment of U.T.M (manufacturer: Instron, model: 4466) is used to stretch the specimen at a crosshead speed of 200 mm / min (1T), the point of the cut specimen is measured and calculated according to the following mathematical formula 1 to obtain the "tensile strength":

[0045] [Mathematical formula 1]

[0046] Tensile strength (kgf / cm 2 ) = load value (kgf) / thickness (cm) × width (cm)

[0047] In the present disclosure, according to the ASTM D638 method, the specimen is stretched at a crosshead speed of 200 mm / min (1T) using U.T.M, the point of the cut specimen is measured and calculated according to the following mathematical formula 2 to obtain the "elongation at break":

[0048] [Mathematical formula 2]

[0049] Elongation at break (%) = length after elongation / initial length × 100

[0050] In the present disclosure, the "migration loss" is obtained according to KSM-3156. By this method, specimens with a thickness of 2 mm or more are obtained, glass plates are attached to both sides of the specimens, and a load of 1 kgf / cm 2 is applied. The specimens are left standing in a hot air circulation type oven (80 °C) for 72 hours, then taken out and cooled at room temperature for 4 hours. Subsequently, the glass plates attached to both sides of the specimens are removed, the weights before and after standing the glass plates and the specimen plates in the oven are measured, and the migration loss is calculated according to the following mathematical formula 3.

[0051] [Mathematical formula 3]

[0052] Migration loss (%) = {[(weight of initial specimen) - (weight of specimen after standing in oven)] / (weight of initial specimen)} × 100

[0053] In the present disclosure, "volatile loss" is obtained by treating a specimen at 80 °C for 72 hours and then measuring the weight of the specimen.

[0054] [Mathematical formula 4]

[0055] Volatile loss (wt%) = {[(weight of initial specimen) - (weight of specimen after treatment)] / (weight of initial specimen)} × 100

[0056] In the case of various measurement conditions, the details of conditions such as temperature, rotation speed, time, etc. can be changed according to circumstances, and if the conditions are different, the measurement method and its conditions need to be indicated separately.

[0057] Hereinafter, the present invention will be explained in more detail to assist in understanding the present invention.

[0058] According to one embodiment of the present invention, a plasticizer composition comprises one or more triesters of the following formula 1, wherein the alkyl groups of the triester are from a carboxylic acid composition comprising a mixture of hexanoic acid isomers and benzoic acid.

[0059] [Formula 1]

[0060]

[0061] In formula 1, R1 to R3 are each independently n-pentyl, branched pentyl, cyclopentyl or phenyl, and R4 and R5 are each independently hydrogen or an alkyl group having 1 to 4 carbon atoms.

[0062] The plasticizer composition can be a product obtained by esterification of a carboxylic acid composition comprising a mixture of hexanoic acid isomers and benzoic acid with a triol, and can thus be from a carboxylic acid having a carbon chain of 6 carbon atoms with a carbonyl as the central carbon. As R1 to R3 of formula 1, a straight-chain, branched or alicyclic alkyl group having 5 carbon atoms can be used, and as a derivative from benzoic acid, phenyl can be used as R1 to R3.

[0063] The plasticizer composition according to one embodiment of the present invention includes one or more triesters represented by formula 1, wherein the number of final produced triesters can be determined according to the amounts of hexanoic acid and benzoic acid contained in the mixture of hexanoic acid isomers used for esterification. For example, if two types of isomers are included in the mixture of hexanoic acid isomers and three types of carboxylic acids are present in the carboxylic acid composition, at least 15 types of triesters can be included in the plasticizer composition.

[0064] In a plasticizer composition according to an embodiment of the present invention, by using an alkyl carboxylic acid having 6 carbon atoms (i.e., hexanoic acid) and benzoic acid simultaneously, the binding force with the resin can be further improved, and the volatilization loss and migration resistance can be improved. In this case, in the carboxylic acid composition, a mixture of hexanoic acid isomers and benzoic acid may be included in a weight ratio of 99:1 to 50:50, where the upper limit may preferably be 95:5, more preferably 90:10, 85:15 or 80:20, and the lower limit may preferably be 55:45, more preferably 60:40, 65:35 or 70:30. If the above range is satisfied, the plasticizing efficiency and elongation at break can be maintained at the level of conventional plasticizers with high performance.

[0065] In addition, if a mixture of hexanoic acid isomers is used, the plasticizing efficiency and mechanical properties can be improved simultaneously compared with the case of using other carbon numbers. If an alkyl carboxylic acid having 5 or less carbon atoms is used, the mechanical properties, volatilization loss and absorption rate may be poor. If an alkyl carboxylic acid having 7 or more carbon atoms is used, the plasticizing efficiency may be poor, the absorption rate may be very slow, and the processability may be significantly deteriorated.

[0066] In addition, considering a compound having three ester groups as a triester, the plasticizer composition has excellent compatibility with the resin and excellent miscibility with other additives, and has many ester groups to fix the molecules in the polymer chain, and thus may have excellent plasticizing efficiency and mechanical properties while maintaining an appropriate level of migration resistance and volatilization loss.

[0067] The alkyl group of the triester included in the plasticizer composition according to an embodiment of the present invention may be derived from a mixture of hexanoic acid isomers having a degree of branching of 2.0 or less. Preferably, the degree of branching is 1.5 or less, 1.3 or less, 1.2 or less, or 1.0 or less. In addition, the degree of branching may be 0.1 or more, 0.2 or more, 0.3 or more.

[0068] Here, the degree of branching may refer to how many branched-chain carbon atoms the alkyl group bonded to the material included in the composition has, and may be determined according to the weight ratio of the corresponding materials. For example, if 60 wt% of 1-hexanoic acid, 30 wt% of 2-methylpentanoic acid, and 10 wt% of 2-ethylbutanoic acid are included in the hexanoic acid mixture, the number of branched-chain carbon atoms of each carboxylic acid is 0, 1, and 2, respectively. The degree of branching can be calculated by [(60×0)+(30×1)+(10×2)] / 100 and can be 0.5. At the same time, in the present invention, the number of branched-chain carbon atoms of cyclopentanecarboxylic acid is considered to be 0.

[0069] Specifically, according to the proportion of branched-chain alkyl groups present in all alkyl groups and further the proportion of specific branched-chain alkyl groups present in the branched-chain alkyl groups, the plasticizing efficiency and the physical properties of migration resistance / volatilization loss can be further balanced, and the processing properties can be optimized. In addition, according to the interaction between various triesters contained in the composition, significant improvements in mechanical properties such as tensile strength and elongation at break and stress resistance can be achieved.

[0070] Thus, a material completely free of environmental problems can be achieved. At the same time, a product with a significantly improved tensile strength compared to conventional phthalate products can be obtained, the migration resistance and stress resistance of conventional terephthalate products can be significantly improved, and a product with balanced physical properties and a significantly higher level compared to conventional commercial products can be obtained. It has been found that the above results can be obtained by combining a C6 alkyl carboxylic acid with benzoic acid as the basic unit of the aromatic carboxylic acid.

[0071] According to one embodiment of the present invention, in order to optimally and advantageously achieve the above effects, a carboxylic acid composition in which the weight ratio range of the mixture of hexanoic acid isomers to benzoic acid is controlled can be employed, and at the same time, the type and amount of the isomers contained in the mixture of hexanoic acid isomers can be controlled.

[0072] The mixture of hexanoic acid isomers may substantially contain 2-methylpentanoic acid and 3-methylpentanoic acid. By substantially containing these two isomers among various isomers in the isomer mixture, the above effects can be achieved with even higher reproducibility.

[0073] In addition, in addition to 2-methylpentanoic acid and 3-methylpentanoic acid, the mixture of hexanoic acid isomers may further contain n-hexanoic acid and cyclopentanecarboxylic acid. In the case of n-hexanoic acid, specific physical properties tend to improve with its inclusion, but considering the processing properties such as the absorption rate or plasticizing efficiency, the amount needs to be controlled, and the same applies to cyclopentanecarboxylic acid.

[0074] In a plasticizer composition according to one embodiment of the present invention, in the mixture of hexanoic acid isomers, relative to a total of 100 parts by weight of the mixture, branched-chain hexanoic acid can be included in an amount of 20 parts by weight or more, 30 parts by weight or more, 40 parts by weight or more, 50 parts by weight or more, and 95 parts by weight or less, 90 parts by weight or less, 85 parts by weight or less, 80 parts by weight or less, or 70 parts by weight or less.

[0075] In addition, relative to a total of 100 parts by weight of the mixture of hexanoic acid isomers, n-hexanoic acid can be included in an amount of 80 parts by weight or less, 70 parts by weight or less, 60 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, or 30 parts by weight or less, and 1 part by weight or more, 2 parts by weight or more, 5 parts by weight or more, or 10 parts by weight or more.

[0076] The contents of the branched type and the linear type can be appropriately controlled according to the application of the triester-based plasticizer, and by controlling the ratio, desired physical properties can be obtained.

[0077] In addition, the isomer mixture may further contain cyclopentanecarboxylic acid, in which case, 30 parts by weight or less of cyclopentanecarboxylic acid may be contained relative to a total of 100 parts by weight of the isomer mixture. Preferably, 20 parts by weight or less, 15 parts by weight or less may be contained. In the case of cyclopentanecarboxylic acid, improvement in processing properties and improvement in mechanical properties can be achieved only when it is contained, and its amount may be controlled in consideration of the deterioration of physical properties caused by the reduction in the relative content of other isomers.

[0078] In the caproic acid isomer mixture that determines the branching degree of the plasticizer composition according to one embodiment of the present invention, various isomers may be included, generally the four types of isomers described, and other isomers may not be excluded. For example, 4-methylpentanoic acid, 2-ethylbutanoic acid, 2,3-dimethylbutanoic acid, etc. may be included, and in addition, structural isomers of C6 alkyl carboxylic acids may be present.

[0079] In addition, the plasticizer composition according to one embodiment of the present invention is derived from the reaction of the carboxylic acid composition including the caproic acid isomer mixture and benzoic acid and a triol, and the triol may be a glycerol compound and may be represented by the following Formula 2, for example.

[0080] [Formula 2]

[0081]

[0082] In Formula 2, R4 and R5 are the same as defined in Formula 1.

[0083] R4 and R5 can each independently be hydrogen or an alkyl group of 1 to 4 carbon atoms, preferably hydrogen, methyl or ethyl, more preferably hydrogen or methyl, and most preferably glycerol in which both R4 and R5 are hydrogen. Considering that glycerol is easily available, can be synthesized from natural materials, and is a material that is easily obtained from other synthetic methods, glycerol can help improve the price competitiveness of the plasticizer.

[0084] The method of preparing the plasticizer composition according to one embodiment of the present invention is a method well known in the art, and any method that can prepare the aforementioned plasticizer composition may be employed without particular limitation.

[0085] That is, by appropriately controlling the esterification reaction, the plasticizer composition according to the present invention can be prepared. For example, the composition can be prepared by direct esterification of a carboxylic acid composition comprising a caproic acid isomer mixture and benzoic acid with a glycerol compound (eg, glycerol) represented by Formula 2.

[0086] The plasticizer composition according to an embodiment of the present invention is a material prepared by appropriately performing an esterification reaction, and any preparation method satisfying the above conditions can be employed without particular limitation. Specifically, the weight ratio of the mixture of hexanoic acid isomers to benzoic acid in the carboxylic acid composition is controlled, and the proportion of branched-chain hexanoic acid in the isomer mixture is controlled.

[0087] For example, the direct esterification can be carried out through the following steps: a step of injecting the carboxylic acid composition and the glycerol compound represented by Formula 2, adding a catalyst and reacting under a nitrogen atmosphere; a step of removing unreacted alcohol and neutralizing unreacted acid; and a step of dehydrating and filtering by distillation under reduced pressure.

[0088] In the case of the carboxylic acid composition, the main function of determining the component ratio in the prepared plasticizer composition can be implemented, and a theoretical molar ratio of 3:1 with the glycerol compound can be employed. If a carboxylic acid composition greater than this molar ratio is additionally injected, the reaction rate can be improved. In this case, the additional injection amount of the carboxylic acid composition can be 400 mol% or less, or 300 mol% or less, preferably 200 mol% or less, or 100 mol% or less, relative to the equivalent of the carboxylic acid composition.

[0089] The catalyst can be, for example, at least one or more selected from acid catalysts such as sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid, p-toluenesulfonic acid, methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, and alkyl sulfates, metal salts such as aluminum lactate, lithium fluoride, potassium chloride, cesium chloride, calcium chloride, iron chloride, and aluminum phosphate, metal oxides such as heteropoly acids, natural / synthetic zeolites, cation exchange resins, and anion exchange resins, and organometals such as tetraalkyl titanates and their polymers. In a specific embodiment, tetraalkyl titanates can be used as the catalyst. Preferably, as acid catalysts with low activation temperatures, p-toluenesulfonic acid and methanesulfonic acid may be suitable.

[0090] The amount of the catalyst can vary depending on the type. For example, based on a total of 100% by weight of the reactants, the homogeneous catalyst can be used in the range of 0.01% to 5.00% by weight, 0.01% to 3.00% by weight, 0.1% to 3.0% by weight, or 0.1% to 2.0% by weight, and based on the total amount of the reactants, the heterogeneous catalyst can be used in the range of 5% to 200% by weight, 5% to 100% by weight, 20% to 200% by weight, or 20% to 150% by weight.

[0091] In this case, the reaction temperature can be 100°C to 280°C, 100°C to 250°C, or 100°C to 230°C.

[0092] According to another embodiment of the present invention, there is provided a resin composition comprising the plasticizer composition and a resin.

[0093] The resin may be a resin known in the art. For example, a mixture of one or more selected from linear vinyl chloride polymers, paste vinyl chloride polymers, ethylene-vinyl acetate copolymers, ethylene polymers, propylene polymers, polyketones, polystyrenes, polyurethanes, natural rubbers, synthetic rubbers, and thermoplastic elastomers may be used without limitation.

[0094] Based on 100 parts by weight of the resin, 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.

[0095] Generally, the resin using the plasticizer composition can be prepared into a resin product by melt processing or plastisol processing, and the resin obtained by melt processing and the resin from plastisol processing can be prepared differently according to each polymerization method.

[0096] For example, in the case of using a vinyl chloride polymer in melt processing, solid resin particles having a large average particle size are prepared and used by suspension polymerization or the like, and this vinyl chloride polymer is called a linear vinyl chloride polymer. In the case of using a vinyl chloride polymer in plastisol processing, a sol-like resin in the form of fine resin particles is prepared and used by emulsion polymerization or the like, and this vinyl chloride polymer is called a paste vinyl chloride resin.

[0097] In the case of a linear vinyl chloride polymer, 5 to 80 parts by weight of a plasticizer may be included based on 100 parts by weight of the polymer, and in the case of a paste vinyl chloride polymer, 40 to 120 parts by weight of a plasticizer may be included based on 100 parts by weight of the polymer.

[0098] The resin composition may further include a filler. Based on 100 parts by weight of the resin, the filler may be 0 to 300 parts by weight, preferably 50 to 200 parts by weight, more preferably 100 to 200 parts by weight.

[0099] The filler may be a filler known in the art and is not particularly limited. For example, the filler may be a mixture of one or more selected from silica, magnesium carbonate, calcium carbonate, anthracite, talc, magnesium hydroxide, titanium dioxide, magnesium oxide, calcium hydroxide, aluminum hydroxide, aluminum silicate, magnesium silicate, and barium sulfate.

[0100] In addition, the resin composition may further include other additives such as stabilizers as needed. Based on 100 parts by weight of the resin, each of the other additives (such as stabilizers) may be, for example, 0 to 20 parts by weight, preferably 1 to 15 parts by weight.

[0101] As the stabilizer, for example, a calcium-zinc-based (Ca-Zn-based) stabilizer such as calcium-zinc composite stearate, or a barium-zinc-based (Ba-Zn-based) stabilizer can be used, but there is no particular limitation.

[0102] The resin composition can be applied to the above-mentioned melt processing and plastisol processing, and casting processing, extrusion processing or injection molding can be applied to the melt processing, and coating processing etc. can be applied to the plastisol processing.

[0103] Example

[0104] Hereinafter, embodiments will be explained in detail to specifically explain the present invention. However, the present invention can be implemented in different forms and should not be construed as being limited to the embodiments described herein. On the contrary, these embodiments are provided so that this disclosure is thorough and complete, and the scope of the inventive concept of the present invention is fully conveyed to those skilled in the art.

[0105] Example 1

[0106] 1360 g of a carboxylic acid composition including a mixture of hexanoic acid isomers (including about 9 wt% of 1-hexanoic acid, about 35 wt% of 2-methylpentanoic acid, about 44 wt% of 3-methylpentanoic acid, about 7 wt% of 4-methylpentanoic acid, and about 5 wt% of cyclopentanecarboxylic acid) and benzoic acid in a weight ratio of 70:30, 276 g of glycerol, and 5 g of methanesulfonic acid were added to a reactor equipped with a stirrer, a condenser, and a decanter, and an esterification reaction was carried out at a reaction temperature of 100°C to 140°C under a nitrogen atmosphere. After the reaction was completed, the unreacted acids were removed, the catalyst and the product were neutralized with an aqueous alkaline solution, and washed. The unreacted raw materials and water were separated, and finally a triester-based plasticizer composition was obtained.

[0107] Example 2

[0108] A triester-based plasticizer composition was obtained in the same manner as in Example 1, except that a mixture including about 20 wt% of 1-hexanoic acid, about 30 wt% of 2-methylpentanoic acid, about 35 wt% of 3-methylpentanoic acid, about 5 wt% of 4-methylpentanoic acid, and about 10 wt% of cyclopentanecarboxylic acid was used as the mixture of hexanoic acid isomers.

[0109] Example 3

[0110] A triester-based plasticizer composition was obtained in the same manner as in Example 1, except that a mixture including about 2 wt% of 1-hexanoic acid, about 40 wt% of 2-methylpentanoic acid, about 50 wt% of 3-methylpentanoic acid, about 2 wt% of 4-methylpentanoic acid, and about 6 wt% of cyclopentanecarboxylic acid was used as the mixture of hexanoic acid isomers.

[0111] Example 4

[0112] A triester-based plasticizer composition was obtained by the same method as in Example 1, except that a mixture comprising about 5 wt% of 1-hexanoic acid, about 50 wt% of 2-methylvaleric acid, about 30 wt% of 3-methylvaleric acid, and about 15 wt% of cyclopentanecarboxylic acid was used as the hexanoic acid isomer mixture.

[0113] Example 5

[0114] A triester-based plasticizer composition was obtained by the same method as in Example 1, except that 1360 g of a carboxylic acid composition comprising a hexanoic acid isomer mixture and benzoic acid in a weight ratio of 90:10 was used.

[0115] Example 6

[0116] A triester-based plasticizer composition was obtained by the same method as in Example 1, except that 1360 g of a carboxylic acid composition comprising a hexanoic acid isomer mixture and benzoic acid in a weight ratio of 80:20 was used.

[0117] Example 7

[0118] A triester-based plasticizer composition was obtained by the same method as in Example 1, except that 1360 g of a carboxylic acid composition comprising a hexanoic acid isomer mixture and benzoic acid in a weight ratio of 60:40 was used.

[0119] Example 8

[0120] A triester-based plasticizer composition was obtained by the same method as in Example 1, except that 1360 g of a carboxylic acid composition comprising a hexanoic acid isomer mixture and benzoic acid in a weight ratio of 50:50 was used.

[0121] Comparative Example 1

[0122] Dioctyl phthalate (DOP, LG Chem) was used as the plasticizer.

[0123] Comparative Example 2

[0124] Diisononyl phthalate (DINP, LG Chem) was used as the plasticizer.

[0125] Comparative Example 3

[0126] GL300, a product of LG Chem and dioctyl terephthalate, was used as the plasticizer.

[0127] Comparative Example 4

[0128] GL500, a product of LG Chem and a mixture of dioctyl terephthalate, butyl octyl terephthalate, and dioctyl terephthalate, was used as the plasticizer.

[0129] Comparative Example 5

[0130] A triester-based plasticizer composition was obtained by the same method as in Example 1, except that an acid mixture obtained by mixing n-butyric acid and benzoic acid in a weight ratio of 7:3 was used in place of the isomeric hexanoic acid mixture.

[0131] Comparative Example 6

[0132] A triester-based plasticizer composition was obtained by the same method as in Example 1, except that a carboxylic acid composition containing only the isomeric hexanoic acid mixture and not containing benzoic acid was used.

[0133] Comparative Example 7

[0134] A triester-based plasticizer composition was obtained by the same method as in Example 1, except that 2-ethylhexanoic acid was used in place of the isomeric hexanoic acid mixture.

[0135] The types and amounts of acids used in the examples and comparative examples are summarized in Table 1 below.

[0136] [Table 1]

[0137]

[0138] Experimental Example 1: Evaluation of sheet properties

[0139] Specimens were manufactured according to ASTM D638 and the following formulation and manufacturing conditions using the plasticizers of the examples and comparative examples.

[0140] (1) Formulation: 100 parts by weight of linear vinyl chloride polymer (LS100), 50 parts by weight of plasticizer, and 3 parts by weight of stabilizer (BZ-153T)

[0141] (2) Mixing: Mixing at 98 °C at 700 rpm

[0142] (3) Manufacturing specimens: 1T, 2T, and 3T sheets were manufactured by treating with a rolling mill at 160 °C for 4 minutes, and treating with a press at 180 °C for 2.5 minutes (low pressure) and 2 minutes (high pressure).

[0143] (4) Test items

[0144] 1) Hardness: Using ASTM D2240, the Shore hardness (Shore "A" and "D") at 25 °C was measured for the 3T specimens within 10 seconds. If the value is small, the plasticizing efficiency is evaluated as excellent.

[0145] 2) Tensile strength:Using the ASTM D638 method, the test specimen was stretched at a crosshead speed of 200 mm / min using a U.T.M. test device (manufacturer: Instron, model: 4466), and the point where the 1T specimen was cut was measured. The tensile strength was calculated by the following mathematical formula 1.

[0146] [Mathematical formula 1]

[0147] Tensile strength (kgf / cm 2 ) = Load value (kgf) / Thickness (cm) × Width (cm)

[0148] 3) Elongation measurement: Using the ASTM D638 method, the test specimen was stretched at a crosshead speed of 200 mm / min using a U.T.M. test device, and the point where the 1T specimen was cut was measured. The elongation was calculated by the following mathematical formula 2.

[0149] [Mathematical formula 2]

[0150] Elongation (%) = Length after elongation / Initial length × 100

[0151] 4) Migration loss measurement: According to KSM-3156, specimens with a thickness of 2 mm or more were obtained. Glass plates were attached to both sides of the 1T specimens, and a load of 1 kgf / cm 2 was applied. The specimens were left in a hot air circulation type oven (80 °C) for 72 hours, then taken out and cooled at room temperature for 4 hours. Subsequently, before and after leaving the glass plates and the test specimens in the oven, the weights of the specimens from which the glass plates attached to both sides were removed were measured, and the migration loss was calculated by the following mathematical formula 3.

[0152] [Mathematical formula 3]

[0153] Migration loss (%) = [((Initial specimen weight) - (Specimen weight after standing in the oven)) / (Initial specimen weight)] × 100

[0154] 5) Volatile loss measurement: The manufactured specimens were treated at 80 °C for 72 hours, the weights of the specimens were measured, and the measurement was carried out by the following mathematical formula 4.

[0155] [Mathematical formula 4]

[0156] Volatile loss (weight %) = [((Initial specimen weight) - (Specimen weight after treatment)) / (Initial specimen weight)] × 100

[0157] 6) Stress test (stress resistance):A specimen with a thickness of 2 mm in a bent state was allowed to stand at 23 °C for 168 hours, and the degree of migration (exudation degree) was observed. The result was recorded as a numerical value, and if this value was close to 0, it indicated excellent performance.

[0158] 7) Absorption rate measurement

[0159] The absorption rate was evaluated by measuring the time consumed for stabilizing the mixer torque by mixing a mixed resin and an ester compound using a planetary mixer (Brabender, P600) at 73 °C and 60 rpm. As a reference, if the measured absorption rate was less than 4 minutes, it seemed that the absorption and migration of the plasticizer were repeated during the processing, and if the absorption rate was greater than 9 minutes, it was considered that the absorption itself hardly occurred. Therefore, if a value between 4 minutes and 9 minutes was not measured, it would be evaluated as not processable.

[0160] (5) Evaluation results

[0161] The evaluation results of the test items are shown in Table 2 below.

[0162] [Table 2]

[0163]

[0164]

[0165] Referring to the results in Table 2, it can be confirmed that when compared with Comparative Examples 1 to 2 which are conventional phthalate products, the plasticizer composition of the present invention shows good plasticizing efficiency, excellent tensile strength and elongation at an equivalent level, and significantly improved absorption rate, and even when compared with Comparative Examples 3 and 4 which are eco-friendly products, great improvements are observed in terms of tensile strength, absorption rate, plasticizing efficiency, migration loss and volatilization loss, and stress resistance. In addition, through excellent physical properties and without deteriorating any one of the properties at the same time, it can be confirmed that the plasticizer composition of the present invention is suitable for mass production and is a stable product.

[0166] In addition, it can be confirmed that when compared with the plasticizers of Comparative Examples 1 and 2 (which are conventional phthalate plasticizers with high performance but causing fatal environmental problems), the plasticizer composition of the present invention achieves an equal or better level and is very suitable as a substitute.

[0167] In addition, compared with the embodiments of the present invention, Comparative Example 5 (wherein the esterification product of glycerol and an acid is used, but a mixture of n-butyric acid and benzoic acid is used instead of a mixture of hexanoic acid isomers and benzoic acid as the acid) showed a significantly lower elongation at break, and showed significantly worse results in terms of volatile loss compared with the embodiments of the present invention. In addition, in the case of Comparative Example 5, in the test for measuring the absorption rate, results indicating non-processability were shown.

[0168] In addition, Comparative Example 6 (wherein only a mixture of hexanoic acid isomers is used without using benzoic acid) showed significantly worse tensile strength, migration loss, and volatile loss compared with the examples. From this result, it can be confirmed that the plasticizer composition of the present invention can achieve improved effects by applying benzoic acid and hexanoic acid simultaneously compared with the case of using only one of them.

[0169] Meanwhile, Comparative Example 7 (wherein 2-ethylhexanoic acid, which is an acid having 8 carbon atoms, is used instead of hexanoic acid) showed worse plasticizing efficiency, elongation at break, migration loss, and stress resistance compared with the examples. From this result, it can be confirmed that in order to obtain a balance of excellent plasticizing efficiency, mechanical properties, various properties such as stress resistance, and processability, hexanoic acid having 6 carbon atoms needs to be used in the form of an isomer mixture type, and benzoic acid needs to be used together as in the embodiments of the present invention.

[0170] Experimental Example 2: Evaluation of plastisol properties

[0171] Specimens were manufactured according to ASTM D638 and the following formulation and manufacturing conditions using the plasticizers of the examples and comparative examples.

[0172] (1) Formulation: 100 parts by weight of a pasty vinyl chloride polymer (KH-10), 70 parts by weight of a plasticizer, 3 parts by weight of a stabilizer (BZ-119), 3 parts by weight of a foaming agent (AC5000), and 40 parts by weight of a filler (OMYA-10)

[0173] (2) Mixing: Mix for 15 minutes at 1000 rpm

[0174] (3) Test items

[0175] 1) Viscosity : Measured as Brookfield viscosity using a Brookfield (LV type) viscometer, #64 was used as the spindle, the measurement rates were 6 rpm and 60 rpm, and the measurement temperatures were 25 °C and 40 °C.

[0176] (4) Evaluation results

[0177] The evaluation results of the test items are shown in Table 3 below.

[0178] [Table 3]

[0179]

[0180] Referring to the results in Table 3, it can be confirmed that the plasticizer compositions of Examples 1 to 4 showed very low initial viscosities during plastisol processing, were significantly advantageous for processing, and showed small viscosity changes over time, with excellent viscosity stability. However, it was found that Comparative Examples 1 to 4 corresponding to conventional products showed high viscosities themselves, and plastisol processing was very disadvantageous compared to the Examples. In particular, in the case of Comparative Examples 1 to 4, the viscosity changes and the initial viscosity were large, and it was confirmed that the performance was significantly inferior in terms of plastisol processing compared to the plasticizer compositions of the present invention.

[0181] At the same time, it can be confirmed that Comparative Examples 5 and 7 (in which plasticizer compositions similar to those of the present invention were prepared by the esterification reaction of glycerol but using different acids) showed inferior performance in plastisol processing compared to the Examples of the present invention. In particular, in the case of Comparative Example 5 in which n-butyric acid and benzoic acid were mixed and used, the initial viscosity was higher than that of the Examples of the present invention, the processing itself could not be carried out, the viscosity change over time was also high, and the viscosity stability was also deteriorated. In addition, in the case of Comparative Example 7 in which an acid having 8 carbon atoms was used instead of hexanoic acid having 6 carbon atoms, the initial viscosity was also high, the viscosity change over time was also high, and the viscosity stability was also deteriorated.

[0182] At the same time, in the case of Comparative Example 6 (in which only the hexanoic acid isomer mixture used in the Examples of the present invention was used in the hexanoic acid isomer mixture and benzoic acid), good effects were shown in terms of the initial viscosity and viscosity stability, but it was confirmed from the results of the sheet formulation examined above that the migration loss and volatilization loss during the sheet formulation process were significantly poorer.

[0183] From the above results, it can be confirmed that the plasticizer composition of the present invention using a mixture of hexanoic acid isomers having 6 carbon atoms and benzoic acid together can maintain excellent physical properties during the conventional sheet formulation process and can achieve excellent processing performance and viscosity stability in plastisol processing.

Claims

1. A triester-based plasticizer composition, comprising: One or more triesters of the following formula 1, Among them, In formula 1, R1 to R3 are from a carboxylic acid composition comprising a mixture of hexanoic acid isomers and benzoic acid, wherein, relative to a total of 100 parts by weight of the mixture of hexanoic acid isomers, the mixture comprises 20 to 95 parts by weight of branched-chain hexanoic acid, wherein, relative to a total of 100 parts by weight of the mixture of hexanoic acid isomers, the mixture comprises 30 parts by weight or less of cyclopentanecarboxylic acid, and wherein the carboxylic acid composition comprises a mixture of hexanoic acid isomers and benzoic acid in a weight ratio of 90:10 to 50:50: [Formula 1] In formula 1, R1 to R3 are each independently n-pentyl, branched-chain pentyl, cyclopentyl, or phenyl, and R4 and R5 are each independently hydrogen or an alkyl group having 1 to 4 carbon atoms.

2. The plasticizer composition according to claim 1, wherein The mixture of hexanoic acid isomers has a degree of branching of 2.0 or less.

3. The plasticizer composition according to claim 1, wherein The mixture of hexanoic acid isomers comprises 2-methylpentanoic acid and 3-methylpentanoic acid.

4. The plasticizer composition according to claim 1, wherein, The mixture of hexanoic acid isomers comprises 1-hexanoic acid, 2-methylpentanoic acid, 3-methylpentanoic acid, and cyclopentanecarboxylic acid.

5. The plasticizer composition according to claim 1, wherein, R4 and R5 are hydrogen.

6. A resin composition, comprising: 100 parts by weight of a resin; and 5 to 150 parts by weight of the plasticizer composition according to claim 1.

7. The resin composition according to claim 6, wherein, The resin is one or more selected from linear vinyl chloride polymers, paste vinyl chloride polymers, ethylene-vinyl acetate copolymers, ethylene polymers, propylene polymers, polyketones, polystyrenes, polyurethanes, natural rubbers, and synthetic rubbers.

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