Triester-based plasticizer composition and resin composition containing same

Abstract

The present invention provides a triester-based plasticizer composition, characterized by containing a product derived from the esterification reaction of a carboxylic acid composition containing a mixture of hexanoic acid isomers and benzoic acid with a trihydric alcohol. When the plasticizer composition is used in a resin, the mechanical properties, absorption rate, stress transferability, and plasticization efficiency can be significantly improved while maintaining the same levels of migration resistance and heat loss compared to when conventional plasticizers are used.

Description

[Technical field]

[0001] This application claims the benefit of priority based on Korean Patent Application No. 10-2021-0080756 filed on June 22, 2021, the entire contents of which are incorporated herein by reference.

[0002] The present invention relates to a plasticizer composition containing one or more triesters and a resin composition containing the same. [Background technology]

[0003] Plasticizers are usually made by reacting alcohol with polycarboxylic acids such as phthalic acid and adipic acid to form the corresponding esters. In addition, in consideration of domestic and international regulations on phthalate-based plasticizers, which are harmful to the human body, research is being conducted on plasticizer compositions that can replace phthalate-based plasticizers, such as terephthalate-based, adipate-based, and other polymer-based plasticizers.

[0004] Meanwhile, the need for such environmentally friendly products is increasing in the plastisol industry, such as flooring, wallpaper, soft and hard sheets, the calendar industry, and the extrusion / injection compound industry. In order to enhance the quality characteristics, processability, and productivity of each finished product, appropriate plasticizers must be used taking into consideration discoloration, migration, mechanical properties, etc.

[0005] In these diverse areas of use, PVC resin is mixed with secondary materials such as plasticizers, fillers, stabilizers, viscosity reducers, dispersants, defoamers, and foaming agents depending on the characteristics required for each industry, such as tensile strength, elongation, light resistance, migration, gelling properties, and absorption speed.

[0006] For example, when di(2-ethylhexyl) terephthalate (DEHTP), which is relatively inexpensive and is the most widely used plasticizer composition that can be used for PVC, is used, the hardness or sol viscosity is high, the absorption rate of the plasticizer is relatively slow, and the migration and stress migration properties are also poor.

[0007] One possible solution to this problem is to use the product of a transesterification reaction with butanol as a plasticizer in a composition containing DEHTP. However, while this improves the plasticization efficiency, it is inferior in terms of heat loss and thermal stability, and the mechanical properties are somewhat reduced, so there is a need to improve the physical properties. Generally, there is currently no solution other than to compensate for this by mixing it with another secondary plasticizer.

[0008] However, when a secondary plasticizer is used, it is difficult to predict the change in physical properties, which may increase the product cost. Except for certain cases, the improvement in physical properties is not clear, and it may cause problems in compatibility with resins, which are disadvantageous in that unpredictable problems may occur.

[0009] In addition, when a trimellitate-based product such as tri(2-ethylhexyl) trimellitate or triisononyl trimellitate is used to improve the poor migration and weight loss properties of the DEHTP product, the migration and weight loss properties are improved, but the plasticization efficiency is poor and a considerable amount must be added to provide a suitable plasticization effect to the resin. Therefore, it is a relatively expensive product and is not commercially viable.

[0010] Therefore, there is a demand for development of products that solve the environmental problems of existing phthalate-based products, or products that improve the poor physical properties of environmentally friendly products that improve the environmental problems of phthalate-based products. Summary of the Invention [Problem to be solved by the invention]

[0011] The present invention provides a plasticizer composition that contains a triester, which is a product derived from the esterification of a carboxylic acid composition containing a mixture of isomers of hexanoic acid and benzoic acid with a trihydric alcohol, and thereby can maintain the same levels of migration resistance and heat loss as when existing plasticizers are used, while significantly improving mechanical properties, absorption rate, stress migration, and plasticization efficiency, as compared to when existing plasticizers are used. [Means for solving the problem]

[0012] In order to solve the above problems, the present invention provides a plasticizer composition and a resin composition. (1) The present invention provides a triester-based plasticizer composition comprising one or more triesters represented by the following Chemical Formula 1, wherein R1 to R3 in the following Chemical Formula 1 are derived from a carboxylic acid composition including a hexanoic acid isomer mixture and benzoic acid.

[0013] [Chemical formula 1] [ka]

[0014] In the above Chemical Formula 1, R1 to R3 each independently represent an n-pentyl group, a branched pentyl group, a cyclopentyl group, or a phenyl group; R4 and R5 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

[0015] (2) In the present invention, there is provided the plasticizer composition according to (1) above, in which the carboxylic acid composition contains a hexanoic acid isomer mixture and benzoic acid in a weight ratio of 99:1 to 50:50.

[0016] (3) In the present invention, there is provided the plasticizer composition according to (1) or (2) above, wherein the hexanoic acid isomer mixture has a degree of branching of 2.0 or less.

[0017] (4) The present invention provides the plasticizer composition according to any one of (1) to (3) above, wherein the hexanoic acid isomer mixture contains 2-methylpentanoic acid and 3-methylpentanoic acid.

[0018] (5) In the present invention, there is provided the plasticizer composition according to any one of (1) to (4), wherein the hexanoic acid isomer mixture contains 1-hexanoic acid, 2-methylpentanoic acid, 3-methylpentanoic acid, and cyclopentylmethanoic acid.

[0019] (6) The present invention provides the plasticizer composition according to any one of (1) to (5) above, wherein the hexanoic acid isomer mixture contains 20 to 95 parts by weight of branched hexanoic acid per 100 parts by weight of the total mixture.

[0020] (7) The present invention provides the plasticizer composition according to any one of (1) to (6) above, in which the hexanoic acid isomer mixture contains 30 parts by weight or less of cyclopentylmethanoic acid per 100 parts by weight of the total mixture.

[0021] (8) The present invention provides the plasticizer composition according to any one of (1) to (7) above, in which R4 and R5 are hydrogen.

[0022] (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 any one of (1) to (8) above.

[0023] (10) In the present invention, there is provided the resin composition according to (9) above, wherein the resin is at least one selected from the group consisting of straight vinyl chloride polymer, paste vinyl chloride polymer, ethylene-vinyl acetate copolymer, ethylene polymer, propylene polymer, polyketone, polystyrene, polyurethane, natural rubber, and synthetic rubber. Effect of the Invention

[0024] When used in a resin composition, the plasticizer composition according to one embodiment of the present invention can maintain the same level of migration resistance and heat loss as existing plasticizers, and can significantly improve mechanical properties, absorption rate, stress migration, and plasticization efficiency. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0025] The terms and words used in this specification and the claims should not be interpreted in a limited manner to their ordinary or dictionary meanings, but should be interpreted in a manner that is consistent with the technical idea of ​​the present invention, based on the principle that the inventors can appropriately define the concepts of terms in order to best describe their invention.

[0026] Definition of Terms The term "composition" as used herein includes mixtures of materials which comprise the composition, as well as reaction products and decomposition products formed from the materials of the composition.

[0027] The term "isomer" as used in this specification is not intended to distinguish all isomers in the sense of the word, but rather to mean and distinguish structural isomers, i.e., isomers having the same number of carbon atoms but different bonding structures, and does not mean that the isomer is a substance that is distinguished into stereoisomers such as optical isomers or diastereomers.

[0028] The term "straight vinyl chloride polymer" as used herein refers to one type of vinyl chloride polymer, which may be polymerized by suspension polymerization, bulk polymerization, or the like, and which has a porous particulate shape with a large number of pores having sizes of tens to hundreds of micrometers distributed therein, is non-aggregating, and has excellent fluidity.

[0029] The term "paste vinyl chloride polymer" as used herein refers to a type of vinyl chloride polymer, which may be polymerized by fine suspension polymerization, fine seed polymerization, emulsion polymerization, or the like, and refers to a polymer that has poor fluidity and tends to aggregate as fine, dense, void-free particles having a size of tens to thousands of nanometers.

[0030] The terms "comprise", "have" and their derivatives are not intended to exclude the presence of any additional components, steps, or procedures, whether these are specifically disclosed or not. To avoid any uncertainty, all compositions claimed by use of the term "comprise" may include any additional additives, adjuvants, or compounds, whether polymeric or otherwise, unless stated to the contrary. In contrast, the term "consisting essentially of" excludes from the scope of any consecutive description any other component, step, or procedure, except those that are not essential to operability. The term "consisting of" excludes any component, step, or procedure not specifically described or listed.

[0031] Measurement method In this specification, the content analysis of the components in the composition is performed by gas chromatography measurement, and analysis is performed using a gas chromatography device manufactured by Agilent (product name: Agilent 7890 GC, column: HP-5, carrier gas: helium (flow rate 2.4 mL / min), detector: FID, injection amount: 1 uL, initial value: 70°C / 4.2 min, final value: 280°C / 7.8 min, program rate: 15°C / min).

[0032] In this specification, "hardness" refers to the Shore hardness (Shore "A" and / or Shore "D") at 25°C in accordance with ASTM D2240, measured under conditions of 3T 10s, and can be an index for evaluating the plasticization efficiency, with a lower hardness indicating a more excellent plasticization efficiency.

[0033] In this specification, the "tensile strength" is calculated according to the ASTM D638 method by measuring the point at which a test piece breaks after pulling it at a cross head speed of 200 mm / min (1T) using a UTM (manufacturer: Instron, model name: 4466) which is a test device, and calculating it according to the following mathematical formula 1.

[0034] [Mathematical formula 1] Tensile strength (kgf / cm 2 ) = Load value (kgf) / thickness (cm) x width (cm)

[0035] In the present specification, the "elongation rate" is calculated according to the following mathematical formula 2, after measuring the point where a test piece breaks after pulling the test piece at a cross head speed of 200 mm / min (1T) using the UTM in accordance with the ASTM D638 method.

[0036] [Mathematical formula 2] Elongation rate (%) = length after elongation / initial length x 100

[0037] In this specification, the term "migration loss" refers to a test piece having a thickness of 2 mm or more, which is obtained according to KSM-3156, and after attaching glass plates to both sides of the test piece, the test piece is subjected to a pressure of 1 kgf / cm 2 A load of 10 ...

[0038] [Mathematical formula 3] Migration loss (%) = {(initial weight of test piece - weight of test piece after oven exposure) / initial weight of test piece} x 100

[0039] In this specification, the "volatile loss" is measured by measuring the weight of a test piece after heating the test piece at 80°C for 72 hours.

[0040] [Mathematical formula 4] Heat loss (wt%) = {(initial test piece weight - test piece weight after treatment) / initial test piece weight} x 100

[0041] In the case of the various measurement conditions described above, the detailed conditions such as temperature, rotation speed, time, etc. may vary slightly depending on the case, and in the case where they vary, the measurement method and conditions will be specified separately.

[0042] The present invention will now be described in more detail to aid in understanding the invention. According to one embodiment of the present invention, the plasticizer composition includes one or more triesters of the following formula 1, in which the alkyl groups of the triesters are derived from a carboxylic acid composition including a mixture of isomeric hexanoic acids and benzoic acid:

[0043] [Chemical formula 1] [ka]

[0044] In the above Chemical Formula 1, R1 to R3 are each independently an n-pentyl group, a branched pentyl group, a cyclopentyl group, or a phenyl group, and R4 and R5 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

[0045] The plasticizer composition may be a reaction product produced by an esterification reaction between a carboxylic acid composition containing a mixture of isomers of hexanoic acid and benzoic acid and a trihydric alcohol.Therefore, as a group derived from a carboxylic acid having a carbon chain containing a central carbon of a carbonyl group and a carbon number of 6, R1 to R3 in the chemical formula 1 may be a linear, branched, or alicyclic alkyl group having a carbon number of 5, and as a group derived from benzoic acid, R1 to R3 in the chemical formula 1 may be a phenyl group.

[0046] The plasticizer composition according to one embodiment of the present invention includes one or more triesters represented by Chemical Formula 1, and the number of triesters finally generated can be determined depending on the number of hexanoic acids and benzoic acids included in the hexanoic acid isomer mixture used in the esterification reaction. For example, when the hexanoic acid isomer mixture includes two isomers, the carboxylic acid composition includes three carboxylic acids, and therefore the plasticizer composition can include at least 15 triesters.

[0047] The plasticizer composition according to one embodiment of the present invention can exhibit better binding strength with resins and improve heat loss and migration resistance by using an alkyl carboxylic acid having 6 carbon atoms, i.e., hexanoic acid and benzoic acid at the same time. In this case, the carboxylic acid composition may contain a mixture of isomers of hexanoic acid and benzoic acid in a weight ratio of 99:1 to 50:50, and the upper limit may be preferably 95:5, more preferably 90:10, 85:15, or 80:20, and the lower limit may be preferably 55:45, more preferably 60:40, 65:35, or 70:30. When the above range is satisfied, the plasticizing efficiency and elongation rate are maintained at the level of existing high-performance plasticizers.

[0048] In addition, when the hexanoic acid isomer mixture is used, the plasticization efficiency and mechanical properties can be improved at the same time, compared to when other carbon numbers are used. When an alkyl carboxylic acid having 5 or less carbon atoms is used, the mechanical properties, heat loss, and absorption rate are poor, and when an alkyl carboxylic acid having 7 or more carbon atoms is used, the plasticization efficiency is poor, the absorption rate is very slow, and the processability may be significantly deteriorated.

[0049] In addition, since the plasticizer composition is a compound having three ester groups as a triester, it has excellent compatibility with resins and excellent miscibility with other additives. Since the plasticizer composition has many ester groups and the molecules can be fixed in the polymer chain, it can have excellent plasticizing efficiency and mechanical properties while maintaining appropriate levels of migration resistance and heat loss.

[0050] The alkyl group of the triester contained in the plasticizer composition according to one embodiment of the present invention is derived from a hexanoic acid isomer mixture having a branching degree of 2.0 or less, and preferably, the branching degree may be 1.5 or less, 1.3 or less, 1.2 or less, or 1.0 or less, or may be 0.1 or more, 0.2 or more, or 0.3 or more.

[0051] Here, the degree of branching may refer to how many branched carbons the alkyl group bound to a substance contained in the composition has, and the degree of branching may be determined according to the weight ratio of the substance. For example, assuming that a hexanoic acid mixture contains 60% by weight of 1-hexanoic acid, 30% by weight of 2-methylpentanoic acid, and 10% by weight of 2-ethylbutanoic acid, the branched carbon numbers of each carboxylic acid are 0, 1, and 2, respectively, and the branched degree may be calculated as [(60×0)+(30×1)+(10×2)] / 100, which may be 0.5. Meanwhile, in the present invention, the branched carbon number of cyclopentylmethanoic acid is considered to be 0.

[0052] Specifically, depending on the ratio of branched alkyl groups to the total alkyl groups, and in turn the ratio of specific branched alkyl groups to the branched alkyl groups, it is possible to further balance the physical properties of plasticization efficiency and migration resistance / weight loss characteristics, and optimize processability. Furthermore, the interaction of multiple triesters contained in the composition can achieve significant improvements in mechanical properties such as tensile strength and elongation, and stress resistance.

[0053] This makes it possible to realize a product that is not only environmentally friendly, but also significantly improves the tensile strength of existing phthalate-based products, and significantly improves the migration resistance and stress resistance of existing terephthalate-based products, making it possible to realize a product that not only has a balance of physical properties, but also has a significantly improved level compared to existing commercial products. This can be understood as a phenomenon that appears when an alkyl carboxylic acid with six carbon atoms is combined with benzoic acid, which is the basic unit of aromatic carboxylic acids.

[0054] In order to more optimally and preferably realize the above-mentioned effects according to one embodiment of the present invention, a carboxylic acid composition in which the weight ratio range of the hexanoic acid isomer mixture and benzoic acid is controlled may be used, and the type and content of the isomers contained in the hexanoic acid isomer mixture may be controlled.

[0055] The hexanoic acid isomer mixture may essentially contain 2-methylpentanoic acid and 3-methylpentanoic acid. By essentially containing the two isomers among various isomers in the isomer mixture, the above-mentioned effect can be realized with higher reproducibility.

[0056] In addition, the hexanoic acid isomer mixture may further include 1-hexanoic acid and cyclopentyl methanoic acid in addition to 2-methyl pentanoic acid and 3-methyl pentanoic acid. In the case of 1-hexanoic acid, the more it is contained, the more the specific physical properties tend to be improved, but the content needs to be adjusted in consideration of the processability aspects of absorption speed and plasticization efficiency, and the same applies to cyclopentyl methanoic acid.

[0057] In the plasticizer composition according to one embodiment of the present invention, the hexanoic acid isomer mixture may contain branched hexanoic acid in an amount of 20 parts by weight or more, 30 parts by weight or more, 40 parts by weight or more, or 50 parts by weight or more, or 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, based on 100 parts by weight of the total mixture.

[0058] Furthermore, based on a total of 100 parts by weight of the hexanoic acid isomer mixture, 1-hexanoic acid may be contained 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, or may be contained in an amount of 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.

[0059] The branched and linear contents can be appropriately adjusted depending on the intended use of the triester plasticizer, and the desired physical properties can be achieved by adjusting the ratio.

[0060] Furthermore, the isomer mixture may further contain cyclopentyl methanoic acid, and in this case, it may be contained in an amount of 30 parts by weight or less based on the total 100 parts by weight of the isomer mixture. Preferably, it may be contained in an amount of 20 parts by weight or less, and may be contained in an amount of 15 parts by weight or less. In the case of cyclopentyl methanoic acid, as long as it is substantially contained, it is possible to improve processability and mechanical properties, and its content can be adjusted taking into consideration the deterioration of properties due to the relative decrease in the content of other isomers.

[0061] The hexanoic acid isomer mixture that determines the branching degree of the plasticizer composition according to one embodiment of the present invention may include various isomers. Although four isomers are typically mentioned, the presence of other isomers is not excluded. For example, 4-methylpentanoic acid, 2-ethylbutanoic acid, or 2,3-dimethylbutanoic acid may be included, and structural isomers of C6 alkyl carboxylic acids may also be present.

[0062] In addition, the plasticizer composition according to one embodiment of the present invention is derived from a reaction between the carboxylic acid composition containing the above-mentioned hexanoic acid isomer mixture and benzoic acid and a trihydric alcohol, and the trihydric alcohol may be a glycerol-based compound, for example, represented by the following chemical formula 2.

[0063] [Chemical formula 2] [ka]

[0064] In the above Chemical Formula 2, R4 and R5 are defined as in the above Chemical Formula 1. The R4 and R5 may each independently be hydrogen or an alkyl group having 1 to 4 carbon atoms, preferably hydrogen, a methyl group, or an ethyl group, more preferably hydrogen or a methyl group, and most preferably glycerol in which R4 and R5 are both hydrogen. Glycerol is easily available, can be synthesized from natural products, and is a substance that can be easily obtained by other synthesis methods, and therefore can greatly contribute to improving the price competitiveness of plasticizers.

[0065] The method for preparing the plasticizer composition according to an embodiment of the present invention is a method well known in the art, and may be used without any particular limitation as long as it is capable of preparing the above-mentioned plasticizer composition.

[0066] That is, the plasticizer composition according to the present invention can be prepared by appropriately controlling the esterification reaction. For example, the composition can be prepared by directly esterifying a carboxylic acid composition including a mixture of isomers of hexanoic acid and benzoic acid with a glycerol-based compound represented by Chemical Formula 2, e.g., glycerol.

[0067] The plasticizer composition according to one embodiment of the present invention is a material prepared by appropriately carrying out the esterification reaction, and there is no particular limitation on the preparation method as long as it satisfies the above-mentioned conditions, in particular, the weight ratio of the hexanoic acid isomer mixture and benzoic acid in the carboxylic acid composition is controlled, and the proportion of branched hexanoic acid in the isomer mixture is controlled.

[0068] For example, the direct esterification reaction may be carried out by adding a carboxylic acid composition and a glycerol-based compound represented by Chemical Formula 2, adding a catalyst, and reacting the mixture under a nitrogen atmosphere, removing unreacted alcohol and neutralizing unreacted acid, and dehydrating and filtering the mixture by distillation under reduced pressure.

[0069] The carboxylic acid composition can perform a major function of determining the component ratio of the plasticizer composition to be prepared, and can be used in a theoretical molar ratio of 3:1 with the glycerol-based compound, and can contribute to improving the reaction rate when the carboxylic acid composition is added in an amount greater than this molar ratio. In this case, the amount of the carboxylic acid composition added may be 400 mol% or less, or 300 mol% or less, preferably 200 mol% or less, or 100 mol% or less, based on the equivalent amount of the carboxylic acid composition.

[0070] The catalyst may be one or more selected from acid catalysts such as sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid, paratoluenesulfonic acid, methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, and alkylsulfuric acid, metal salts such as aluminum lactate, lithium fluoride, potassium chloride, cesium chloride, calcium chloride, iron chloride, and aluminum phosphate, metal oxides such as heteropolyacids, natural / synthetic zeolites, cation and anion exchange resins, and organic metals such as tetraalkyl titanate and its polymers. As a specific example, tetraalkyl titanate may be used as the catalyst. Preferably, paratoluenesulfonic acid, methanesulfonic acid, and the like are suitable as acid catalysts with low activation temperatures.

[0071] The amount of catalyst used may vary depending on the type, and for example, in the case of a homogeneous catalyst, it may be in the range of 0.01 to 5.00 wt%, 0.01 to 3.00 wt%, 0.1 to 3.0 wt%, or 0.1 to 2.0 wt%, relative to 100 wt% of the total reactants, and in the case of a heterogeneous catalyst, it may be in the range of 5 to 200 wt%, 5 to 100 wt%, 20 to 200 wt%, or 20 to 150 wt% of the total reactants. In this case, the reaction temperature may be within the range of 100 to 280°C, 100 to 250°C, or 100 to 230°C.

[0072] According to another embodiment of the present invention, there is provided a resin composition comprising the plasticizer composition described above and a resin. The resin may be any resin known in the art, such as, but not limited to, a mixture of one or more selected from the group consisting of straight vinyl chloride polymer, paste vinyl chloride polymer, ethylene-vinyl acetate copolymer, ethylene polymer, propylene polymer, polyketone, polystyrene, polyurethane, natural rubber, synthetic rubber, and thermoplastic elastomer.

[0073] 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, based on 100 parts by weight of the resin. Generally, the resins in which the plasticizer composition is used can be manufactured into resin products by melt processing or plastisol processing, and melt-processed resins and plastisol-processed resins may be produced differently depending on the polymerization method.

[0074] For example, when vinyl chloride polymer is used in melt processing, it is produced by suspension polymerization or the like, and solid resin particles with a large average particle size are used, and such vinyl chloride polymer is called straight vinyl chloride polymer, and when it is used in plastisol processing, it is produced by emulsion polymerization or the like, and a resin in a sol state is used as fine resin particles, and such vinyl chloride polymer is called paste vinyl chloride resin.

[0075] In this case, in the case of the straight vinyl chloride polymer, the plasticizer is preferably contained in a range of 5 to 80 parts by weight per 100 parts by weight of the polymer, and in the case of a paste vinyl chloride polymer, the plasticizer is preferably contained in a range of 40 to 120 parts by weight per 100 parts by weight of the polymer.

[0076] The resin composition may further contain a filler, the amount of which may be 0 to 300 parts by weight, preferably 50 to 200 parts by weight, and more preferably 100 to 200 parts by weight, based on 100 parts by weight of the resin.

[0077] The filler may be any filler known in the art and is not particularly limited.For example, it may be a mixture of 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.

[0078] The resin composition may further contain other additives such as a stabilizer, if necessary. The amount of each of the other additives such as a stabilizer may be, for example, 0 to 20 parts by weight, preferably 1 to 15 parts by weight, based on 100 parts by weight of the resin.

[0079] The stabilizer may be, for example, a calcium-zinc (Ca-Zn) stabilizer such as a calcium-zinc complex stearate or a barium-zinc (Ba-Zn) stabilizer, but is not particularly limited thereto.

[0080] The resin composition may be used in both melt processing and plastisol processing as described above. For example, the melt processing may be a calendar process, an extrusion process, or an injection process, and the plastisol processing may be a coating process.

[0081] Working Example The present invention will be described in detail below with reference to examples. However, the examples of the present invention may be modified in various different forms, and the scope of the present invention should not be construed as being limited to the examples described below. The examples of the present invention are provided to more completely explain the present invention to those having average knowledge in the art.

[0082] Example 1 Into a reactor equipped with an agitator, a condenser, and a decanter, 1360 g of a carboxylic acid composition containing a hexanoic acid isomer mixture containing about 9 wt% 1-hexanoic acid, about 35 wt% 2-methylpentanoic acid, about 44 wt% 3-methylpentanoic acid, about 7 wt% 4-methylpentanoic acid, and about 5 wt% cyclopentylmethanoic acid and benzoic acid in a weight ratio of 70:30, 276 g of glycerol, and 5 g of methanesulfonic acid were added, and then an esterification reaction was carried out at a reaction temperature of 100 to 140°C under a nitrogen atmosphere to terminate the reaction, and after removing unreacted acid, the catalyst and the product were neutralized and washed with an alkaline aqueous solution, and unreacted raw materials and water were purified, and finally a triester-based plasticizer composition was obtained.

[0083] Example 2 A triester-based plasticizer composition was obtained in the same manner as in Example 1, except that a mixture containing about 20% by weight of 1-hexanoic acid, about 30% by weight of 2-methylpentanoic acid, about 35% by weight of 3-methylpentanoic acid, about 5% by weight of 4-methylpentanoic acid, and about 10% by weight of cyclopentylmethanoic acid was used as the hexanoic acid isomer mixture.

[0084] Example 3 A triester-based plasticizer composition was obtained in the same manner as in Example 1, except that the hexanoic acid isomer mixture used was a mixture containing about 2 wt % 1-hexanoic acid, about 40 wt % 2-methylpentanoic acid, about 50 wt % 3-methylpentanoic acid, about 2 wt % 4-methylpentanoic acid, and about 6 wt % cyclopentylmethanoic acid.

[0085] Example 4 A triester-based plasticizer composition was obtained in the same manner as in Example 1, except that the hexanoic acid isomer mixture was a mixture containing about 5 wt % 1-hexanoic acid, about 50 wt % 2-methylpentanoic acid, about 30 wt % 3-methylpentanoic acid, and about 15 wt % cyclopentylmethanoic acid.

[0086] Example 5 The same procedure was carried out as in Example 1, except that 1360 g of a carboxylic acid composition containing a hexanoic acid isomer mixture and benzoic acid in a weight ratio of 90:10 was used, to obtain a triester-based plasticizer composition.

[0087] Example 6 The same procedure was carried out as in Example 1, except that 1360 g of a carboxylic acid composition containing a hexanoic acid isomer mixture and benzoic acid in a weight ratio of 80:20 was used, to obtain a triester-based plasticizer composition.

[0088] Example 7 The same procedure was carried out as in Example 1, except that 1360 g of a carboxylic acid composition containing a hexanoic acid isomer mixture and benzoic acid in a weight ratio of 60:40 was used, to obtain a triester-based plasticizer composition.

[0089] Example 8 The same procedure was carried out as in Example 1, except that 1360 g of a carboxylic acid composition containing a hexanoic acid isomer mixture and benzoic acid in a weight ratio of 50:50 was used, to obtain a triester-based plasticizer composition.

[0090] Comparative Example 1 Dioctyl phthalate (DOP, manufactured by LG Chemicals) was used as the plasticizer.

[0091] Comparative Example 2 Diisononyl phthalate (DINP, manufactured by LG Chemicals) was used as the plasticizer.

[0092] Comparative Example 3 As a plasticizer, GL300 manufactured by LG Chemical, which is dioctyl terephthalate, was used.

[0093] Comparative Example 4 As a plasticizer, GL500 manufactured by LG Chemical, which is a mixture of dibutyl terephthalate, butyl octyl terephthalate, and dioctyl terephthalate, was used.

[0094] Comparative Example 5 A triester-based plasticizer composition was obtained in the same manner as in Example 1, except that an acid mixture in which n-butanoic acid and benzoic acid were mixed in a weight ratio of 7:3 was used instead of the hexanoic acid isomer mixture.

[0095] Comparative Example 6 A triester-based plasticizer composition was obtained in the same manner as in Example 1, except that benzoic acid was not used and a carboxylic acid composition containing only a hexanoic acid isomer mixture was used.

[0096] Comparative Example 7 The same procedure as in Example 1 was carried out, except that 2-ethylhexanoic acid was used instead of the hexanoic acid isomer mixture, to obtain a triester plasticizer composition. The types and contents of acids used in the above examples and comparative examples are summarized in Table 1 below.

[0097] [Table 1]

[0098] Experimental example 1: Evaluation of seat performance Using the plasticizers of the Examples and Comparative Examples, test pieces were prepared according to the following recipe and preparation conditions in accordance with ASTM D638.

[0099] (1) Formulation: 100 parts by weight of straight vinyl chloride polymer (LS100), 50 parts by weight of plasticizer, and 3 parts by weight of stabilizer (BZ-153T). (2) Blending: Mix at 98°C and 700 rpm

[0100] (3) Preparation of test pieces: 1T, 2T, and 3T sheets were prepared by treating in a roll mill at 160°C for 4 minutes, and in a press at 180°C for 2.5 minutes (low pressure) and 2 minutes (high pressure).

[0101] (4) Evaluation items 1)Hardness : Shore hardness (Shore "A" and "D") at 25°C was measured for 10 seconds on a 3T test piece in accordance with ASTM D2240. The smaller the value, the better the plasticization efficiency.

[0102] 2) Tensile strength According to ASTM D638, a test device UTM (manufacturer: Instron, model name: 4466) was used to measure the point at which a 1T test piece broke after pulling at a cross head speed of 200 mm / min. The tensile strength was calculated according to the following mathematical formula 1.

[0103] [Mathematical formula 1] Tensile strength (kgf / cm 2 ) = Load value (kgf) / (Thickness (cm) x Width (cm))

[0104] 3) Measurement of elongation rate: According to the ASTM D638 method, the UTM was used to pull the 1T test piece at a cross head speed of 200 mm / min, and the point at which the test piece broke was measured and calculated according to the following Equation 2.

[0105] [Mathematical formula 2] Elongation rate (%) = length after elongation / initial length x 100

[0106] 4) Measurement of migration loss: According to KSM-3156, a test piece with a thickness of 2 mm or more was obtained, and glass plates were attached to both sides of the 1T test piece, and then the test piece was subjected to a pressure of 1 kgf / cm 2A load of 10 ...

[0107] [Mathematical formula 3] Migration loss (%) = [{(initial weight of test piece) - (weight of test piece after leaving in oven)} / (initial weight of test piece)] × 100

[0108] 5) Measurement of volatile loss: The prepared test piece was treated at 80° C. for 72 hours, and then the weight of the test piece was measured and calculated according to the following Equation 4.

[0109] [Mathematical formula 4] Heat loss (wt%) = [{(initial weight of test piece) - (weight of test piece after treatment)} / (initial weight of test piece)] x 100

[0110] 6) Stress test (stress resistance): A 2mm thick test piece was left in a bent state at 23°C for 168 hours, after which the degree of migration (exudation) was observed and the results were expressed as a number, with the closer to 0 the better the characteristics.

[0111] 7) Measurement of absorption rate The absorption rate was measured using a planetary mixer (Brabender, P600) at 73℃ and 60 rpm, and was the time required for the resin and ester compound to be mixed together and for the torque of the mixer to stabilize. For reference, if the absorption rate is measured as less than 4 minutes, it can be considered that the absorption and migration of the plasticizer occurs repeatedly during processing, and if it exceeds 9 minutes, it can be considered that the absorption itself is not smooth, so if it is not measured as a value between 4 and 9 minutes, it is evaluated as not processable.

[0112] (5) Evaluation results The evaluation results for the above items are shown in Table 2 below.

[0113] [Table 2]

[0114] Referring to the results in Table 2, it can be confirmed that, compared to the existing phthalate-based products of Comparative Examples 1 and 2, the tensile strength is excellent, and the elongation is at the same level, yet the plasticization efficiency is also excellent, and the absorption speed is remarkably improved, and even compared to the environmentally friendly products of Comparative Examples 3 and 4, significant improvements were observed in the tensile strength, absorption speed, plasticization efficiency, migration loss, heat loss, and stress resistance. In addition, since none of the physical properties were evaluated as being inferior, and were confirmed to be excellent, it can be confirmed that the product is suitable for mass production and has stable performance.

[0115] In addition, it was confirmed that the new plasticizer achieves a level equal to or higher than that of the plasticizers in Comparative Examples 1 and 2, which are high-performance but cause serious environmental problems as existing phthalate plasticizers, and it can be confirmed that the new plasticizer is very suitable as an alternative plasticizer.

[0116] Comparative Example 5, which uses an esterification product of glycerol and an acid, but uses a mixture of n-butanoic acid and benzoic acid as the acid, instead of a mixture of a mixture of hexanoic acid isomers and benzoic acid, showed a significantly lower elongation rate than the examples of the present invention, and also showed a significantly inferior result in terms of heat loss compared to the examples of the present invention. Furthermore, in the case of Comparative Example 5, the absorption rate measurement experiment also showed a result of being unprocessable.

[0117] In addition, Comparative Example 6, in which only a mixture of hexanoic acid isomers was used as an acid without benzoic acid, was inferior to the Examples in terms of tensile strength, migration loss, and heat loss. From this, it can be confirmed that the plasticizer composition of the present invention can achieve improved effects by using benzoic acid and hexanoic acid simultaneously, compared to the case where only one of them is used.

[0118] On the other hand, Comparative Example 7, in which 2-ethylhexanoic acid, an acid having 8 carbon atoms, was used instead of hexanoic acid, was inferior to the Examples in terms of plasticization efficiency, elongation, migration loss, and stress resistance. From this, it was confirmed that in order to achieve a good balance of various physical properties such as plasticization efficiency, mechanical properties, stress resistance, and processability, hexanoic acid having 6 carbon atoms must be used in the form of an isomer mixture together with benzoic acid, as in the Examples of the present invention.

[0119] Example 2: Evaluation of plastisol performance Using the plasticizers of the Examples and Comparative Examples, test pieces were prepared according to the following recipe and preparation conditions in accordance with ASTM D638.

[0120] (1) Formulation: Paste: 100 parts by weight of vinyl chloride polymer (KH-10), 70 parts by weight of plasticizer, 3 parts by weight of stabilizer (BZ-119), 3 parts by weight of foaming agent (AC5000), and 40 parts by weight of filler (OMYA-10). (2) Blending: Mix at 1000 rpm for 15 minutes

[0121] (3) Evaluation items 1) Viscosity: The Brookfield viscosity was measured using a Brookfield (LV type) viscometer, using a #64 spindle, at measurement speeds of 6 rpm and 60 rpm, and at measurement temperatures of 25°C and 40°C.

[0122] (4) Evaluation results The evaluation results for the above items are shown in Table 3 below.

[0123] [Table 3]

[0124] Referring to the results in Table 3, it can be seen that in the case of Examples 1 to 4, the plasticizer compositions have a very low initial viscosity during plastisol processing, which is quite advantageous for processing, and there is little change in viscosity over time, resulting in excellent viscosity stability. On the other hand, it can be seen that in the case of Comparative Examples 1 to 4, which correspond to the existing product group, the viscosity itself is high, which makes plastisol processing less advantageous compared to the Examples. In particular, in the case of Comparative Examples 1 and 4, not only the initial viscosity but also the range of change in viscosity is large, which confirms that the performance is significantly reduced in plastisol processing compared to the plasticizer composition of the present invention.

[0125] On the other hand, it was confirmed that Comparative Examples 5 and 7, which were produced by esterification of glycerol like the plasticizer composition of the present invention but used an acid different from that of the present invention, also had a lower performance in plastisol processing compared to the examples of the present invention. Specifically, it was confirmed that in the case of Comparative Example 5, in which a mixture of n-butanoic acid and benzoic acid was used, the initial viscosity was higher than that of the examples of the present invention, the processing itself was disadvantageous, the viscosity change over time was large, and the viscosity stability was also reduced. In addition, it was confirmed that Comparative Example 7, in which an acid having 8 carbon atoms was used instead of hexanoic acid having 6 carbon atoms, also showed a high initial viscosity, the viscosity change over time was large, and the viscosity stability was also reduced.

[0126] On the other hand, in the case of Comparative Example 6, in which only the isomer mixture of hexanoic acid was used among the isomer mixture of hexanoic acid and benzoic acid used in the examples of the present invention, the initial viscosity and viscosity stability were satisfactory, but as can be seen from the above-mentioned sheet formulation results, the migration loss during sheet formulation and the heat loss were very poor.

[0127] From this, it was confirmed that the plasticizer composition of the present invention, by using both a mixture of C6 hexanoic acid isomers and benzoic acid, can achieve excellent processability and viscosity stability in plastisol processing while maintaining the excellent physical properties of existing sheet formulations.

Claims

1. The compound includes one or more triesters represented by the following formula 1: R in the following formula 1 １ ~R ３ is a triester plasticizer composition derived from a carboxylic acid composition including a mixture of isomeric hexanoic acids and benzoic acid. [Chemical formula 1] 【Chemistry 1】 In the above Chemical Formula 1, R ４ and R ５ are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, The carboxylic acid composition includes an isomeric mixture of hexanoic acid and benzoic acid in a weight ratio of 90:10 to 50:

50.

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

3. 2. The plasticizer composition of claim 1, wherein the hexanoic acid isomer mixture comprises 2-methylpentanoic acid and 3-methylpentanoic acid.

4. 2. The plasticizer composition of claim 1, wherein the hexanoic acid isomer mixture comprises 1-hexanoic acid, 2-methylpentanoic acid, 3-methylpentanoic acid, and cyclopentylmethanoic acid.

5. 2. The plasticizer composition of claim 1, wherein the hexanoic acid isomer mixture contains 20 to 95 parts by weight of branched hexanoic acid per 100 parts by weight of the total mixture.

6. 2. The plasticizer composition of claim 1, wherein the hexanoic acid isomer mixture comprises 30 parts by weight or less of cyclopentyl methanoic acid per 100 parts by weight of the total mixture.

7. The R ４ and R ５ The plasticizer composition of claim 1 , wherein is hydrogen.

8. 100 parts by weight of resin; 5 to 150 parts by weight of the plasticizer composition according to claim 1; A resin composition comprising:

9. 9. The resin composition according to claim 8, wherein the resin is at least one selected from the group consisting of straight vinyl chloride polymer, paste vinyl chloride polymer, ethylene-vinyl acetate copolymer, ethylene polymer, propylene polymer, polyketone, polystyrene, polyurethane, natural rubber, and synthetic rubber.

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