Propane tricarboxylate plasticizer composition and resin composition containing the same

Abstract

The present invention is characterized in that the propane tricarboxylate has an alkyl group derived from an isomeric mixture of hexyl alcohol, and when applied to a resin, it has high plasticization efficiency and can achieve excellent tensile properties, elongation properties, migration resistance, heat loss and stress resistance.

Description

[Technical field]

[0001] The present invention relates to a plasticizer composition containing a propane tricarboxylate having alkyl groups of various structures within the same carbon number, and a resin composition containing the same. [Background technology]

[0002] 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 ongoing into plasticizer compositions that can be used to replace phthalate-based plasticizers, such as terephthalate-based, adipate-based, and other polymer-based plasticizers.

[0003] Meanwhile, the need for such environmentally friendly products is increasing in the plastisol industry, including flooring, wallpaper, soft and hard sheets, the calendaring industry, and the extrusion / injection compounding industry. In order to enhance the quality characteristics, processability, and productivity of each finished product, it is necessary to use appropriate plasticizers taking into consideration discoloration, migration, mechanical properties, etc.

[0004] In these various areas of use, PVC resin is mixed with auxiliary 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.

[0005] For example, when di(2-ethylhexyl) terephthalate (DEHTP), which is relatively inexpensive and most widely used among plasticizer compositions applicable to PVC, is applied, 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.

[0006] 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, although this would improve the plasticization efficiency, it would be necessary to improve the physical properties, such as poor heat loss and thermal stability, and some deterioration in mechanical properties. Generally, there is currently no solution other than to supplement this by mixing it with another secondary plasticizer.

[0007] However, when using secondary plasticizers, it is difficult to predict the changes in physical properties, which may increase the product price. In addition, improvements in physical properties are not clearly demonstrated except in specific cases, and unpredictable problems such as compatibility issues with resins may occur.

[0008] 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 reduced and a considerable amount must be added to provide an appropriate plasticization effect to the resin. Therefore, the product is relatively expensive and cannot be commercially used.

[0009] 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]

[0010] The present invention aims to provide a plasticizer composition that contains propane tricarboxylate in which an alkyl group is derived from an isomer mixture of hexyl alcohol, thereby maintaining mechanical properties and stress resistance at levels equal to or higher than those of existing plasticizers, and improving migration and plasticization efficiency. [Means for solving the problem]

[0011] In order to solve the above problems, the present invention provides a plasticizer composition and a resin composition containing the plasticizer composition.

[0012] Specifically, (1) the present invention provides a propane tricarboxylate-based composition including one or more propane tricarboxylates represented by the following Chemical Formula 1, wherein the alkyl group of the propane tricarboxylate is derived from an isomeric mixture of hexyl alcohol, and the isomeric mixture of hexyl alcohol includes two or more selected from the group consisting of 1-hexanol, 1-methylpentanol, 2-methylpentanol, 3-methylpentanol, 4-methylpentanol, 1,1-dimethylbutanol, 1,2-dimethylbutanol, 1,3-dimethylbutanol, 2,2-dimethylbutanol, 2,3-dimethylbutanol, 3,3-dimethylbutanol, 1-ethylbutanol, 2-ethylbutanol, 3-ethylbutanol, and cyclopentylmethanol. [Chemical formula 1] [ka] In the above Chemical Formula 1, R1 to R3 are each independently an n-hexyl group, a branched hexyl group, or a cyclopentylmethyl group.

[0013] (2) The present invention provides the plasticizer composition according to (1) above, wherein the mixture of hexyl alcohol isomers has a degree of branching of 2.0 or less.

[0014] (3) The present invention provides the plasticizer composition according to (1) or (2) above, wherein the mixture of hexyl alcohol isomers has a degree of branching of 1.5 or less.

[0015] (4) The present invention provides a plasticizer composition according to any one of the above (1) to (3), wherein the mixture of hexyl alcohol isomers contains 1-hexanol, 2-methylpentanol, and 3-methylpentanol.

[0016] (5) The present invention provides a plasticizer composition according to any one of the above items (1) to (4), wherein the isomer mixture of hexyl alcohol contains 40 parts by weight or more of a branched alcohol per 100 parts by weight of the isomer mixture.

[0017] (6) The present invention provides a plasticizer composition according to any one of the above items (1) to (5), wherein the isomer mixture of hexyl alcohol contains 50 to 95 parts by weight of a branched alcohol per 100 parts by weight of the isomer mixture.

[0018] (7) The present invention provides a plasticizer composition according to any one of the above items (1) to (6), wherein the isomer mixture of hexyl alcohol contains 40 parts by weight or less of 1-hexanol per 100 parts by weight of the isomer mixture.

[0019] (8) The present invention provides a plasticizer composition in any one of the above (1) to (7), wherein the mixture of hexyl alcohol isomers contains 1-hexanol, 2-methylpentanol, 3-methylpentanol, and cyclopentylmethanol.

[0020] (9) The present invention provides the plasticizer composition according to any one of the above items (1) to (8), wherein the isomer mixture of hexyl alcohol contains 20 parts by weight or less of cyclopentylmethanol per 100 parts by weight of the isomer mixture.

[0021] (10) 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 (9) above.

[0022] (11) The present invention provides a resin composition according to (10) 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, polylactic acid, natural rubber, and synthetic rubber. Effect of the Invention

[0023] When used in a resin composition, the plasticizer composition according to one embodiment of the present invention can maintain or improve mechanical properties and stress resistance to levels equal to or greater than those of existing plasticizers, and can improve physical properties such as weight loss characteristics and plasticization efficiency. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0024] 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.

[0025] 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.

[0026] 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 the form of porous particles in which a large number of pores having sizes of tens to hundreds of micrometers are distributed, is non-aggregating, and has excellent fluidity.

[0027] 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.

[0028] The terms "comprising," "having," 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 "comprising" 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 sequential 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.

[0029] Measurement method In this specification, the content of components in a composition is analyzed by gas chromatography measurement 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 volume: 1 μL, initial value: 70° C. / 4.2 min, final value: 280° C. / 7.8 min, program rate: 15° C. / min).

[0030] In this specification, "hardness" refers to 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 plasticization efficiency, with a lower hardness indicating a more excellent plasticization efficiency.

[0031] In this specification, the "tensile strength" is calculated according to the ASTM D638 method by measuring the point where a test piece breaks after pulling it at a cross head speed of 200 mm / min (1T) using a UTM (manufacturer: Instron, model: 4466) which is a test device, and calculating it according to the following mathematical formula 1.

[0032] [Mathematical formula 1] Tensile strength (kgf / cm2) = load value (kgf) / thickness (cm) x width (cm)

[0033] In the present specification, the "elongation rate" is calculated by 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, and calculating the elongation rate according to the following mathematical formula 2.

[0034] [Mathematical formula 2] Elongation rate (%) = length after elongation / initial length x 100

[0035] In this specification, the "migration loss" is calculated by obtaining a test specimen with a thickness of 2 mm or more according to KSM-3156, attaching a glass plate to both sides of the test specimen, and applying a load of 1 kgf / cm2. The test specimen is left in a hot air circulating oven (80°C) for 72 hours, then removed and cooled at room temperature for 4 hours. After that, the glass plates attached to both sides of the test specimen are removed, and the weights of the glass plates and the specimen plate before and after leaving them in the oven are measured, and the amount of migration loss is calculated according to the following mathematical formula 3.

[0036] [Mathematical formula 3] Migration loss (%) = {(initial weight of test piece) - (weight of test piece after leaving in oven) / (initial weight of test piece)} x 100

[0037] In this specification, the "volatile loss" is measured by measuring the weight of a test piece after working the test piece at 80°C for 72 hours.

[0038] [Mathematical formula 4] Heat loss (%) = {(initial weight of test piece) - (weight of test piece after processing) / (initial weight of test piece)} x 100

[0039] In the case of the various measurement conditions, the detailed conditions such as temperature, rotation speed, time, etc. may vary slightly depending on the case, and if they do vary, the measurement method and conditions will be separately specified.

[0040] In the following, the present invention will be described in more detail in order to facilitate understanding of the present invention.

[0041] According to one embodiment of the present invention, there is provided a tricarboxylate-based plasticizer composition comprising one or more propane tricarboxylates represented by the following Chemical Formula 1, wherein the alkyl group of the propane tricarboxylate is derived from an isomeric mixture of hexyl alcohol, and the isomeric mixture of hexyl alcohol comprises two or more selected from the group consisting of 1-hexanol, 1-methylpentanol, 2-methylpentanol, 3-methylpentanol, 4-methylpentanol, 1,1-dimethylbutanol, 1,2-dimethylbutanol, 1,3-dimethylbutanol, 2,2-dimethylbutanol, 2,3-dimethylbutanol, 3,3-dimethylbutanol, 1-ethylbutanol, 2-ethylbutanol, 3-ethylbutanol, and cyclopentylmethanol.

[0042] [Chemical formula 1] [ka]

[0043] In the above Chemical Formula 1, R1 to R3 are each independently an n-hexyl group, a branched hexyl group, or a cyclopentylmethyl group.

[0044] The plasticizer composition may be a product produced by a direct esterification reaction between 1,2,3-propanetricarboxylic acid or a derivative thereof and a hexyl alcohol mixture, or a transesterification reaction between a trialkyl 1,2,3-tricarboxylate and a hexyl alcohol mixture, and the mixture of hexyl alcohols used in this case may be a mixture of hexyl alcohols having different structures, i.e., a mixture of structural isomers. More specifically, the isomer mixture of hexyl alcohols may include two or more selected from the group consisting of 1-hexanol, 1-methylpentanol, 2-methylpentanol, 3-methylpentanol, 4-methylpentanol, 1,1-dimethylbutanol, 1,2-dimethylbutanol, 1,3-dimethylbutanol, 2,2-dimethylbutanol, 2,3-dimethylbutanol, 3,3-dimethylbutanol, 1-ethylbutanol, 2-ethylbutanol, 3-ethylbutanol, and cyclopentylmethanol.

[0045] The alkyl groups R1 to R3 in Chemical Formula 1 can be determined according to the alcohol contained in the hexyl alcohol isomer, and the final composition can include various compositions in which three, two, or one isomeric alkyl group of hexyl alcohol is bonded to each of the three alkyl groups, and the ratio of components in the final composition can be determined according to the ratio of each structural isomer component in the reacted hexyl alcohol mixture.

[0046] In this way, when an alcohol having 6 carbon atoms is used in applying a tricarboxylate-based plasticizer, it is possible to provide better mechanical properties than an alcohol having less than 6 carbon atoms, more specifically, it is possible to significantly improve tensile strength, elongation, and heat loss, and it is possible to provide better plasticization efficiency, migration resistance, and stress resistance than when the carbon number exceeds 6.

[0047] The branching degree of the hexyl alcohol isomer mixture of the plasticizer composition according to one embodiment of the present invention may be 2.0 or less, preferably 1.5 or less. Specifically, the branching degree may be 1.5 or less, 1.3 or less, more preferably 1.1 or less, and particularly preferably 1.0 or less. It may also be 0.1 or more, 0.2 or more, 0.3 or more, and most preferably 0.7 or more. The branching degree of the hexyl alcohol isomer mixture may be similarly maintained in the tricarboxylate-based plasticizer composition produced from hexyl alcohol. If the branching degree is too high, the balance between the physical properties may be lost, resulting in a problem that the product does not meet one or more evaluation criteria. However, when the branching degree is 1.5 or less as a preferred range, the improvement of not only the mechanical properties but also the migration loss and the heat loss may be more optimized, and the balance between the physical properties may be excellent.

[0048] 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 an alcohol mixture contains 60% by weight of n-hexyl alcohol, 30% by weight of methyl pentanol, and 10% by weight of ethyl butanol, the branched carbon numbers of each alcohol are 0, 1, and 2, respectively, and the degree of branching may be calculated as [(60×0)+(30×1)+(10×2)] / 100, which is 0.5. Meanwhile, in defining the degree of branching in the present invention, the number of branched carbons in the case of cyclopentyl methanol is considered to be 0.

[0049] The hexyl alcohol isomer mixture may contain 1-hexanol and 2-methylpentanol. When the isomer mixture contains both 1-hexanol and 2-methylpentanol, the balance between the physical properties can be maintained, and an excellent effect can be obtained in terms of heat loss. Preferably, the isomer mixture may further contain 3-methylpentanol, which has the advantage of having an excellent balance between the physical properties.

[0050] The branched hexyl alcohol including 2-methylpentanol may be included in an amount of 40 parts by weight or more, 50 parts by weight or more, 60 parts by weight or more, and preferably 65 parts by weight or more, 70 parts by weight or more, based on 100 parts by weight of the isomer mixture. The maximum amount may be entirely branched, and may be 99 parts by weight or less, 98 parts by weight or less, and preferably 95 parts by weight or less, or 90 parts by weight or less. When the branched hexyl alcohol is included within this range, improvement in mechanical properties can be expected.

[0051] In addition, the linear alcohol of 1-hexanol may be included in an amount of 50 parts by weight or less, 40 parts by weight or less, and preferably 30 parts by weight or less, based on 100 parts by weight of the isomer mixture. The 1-hexanol may not be present in the component, but may be included in an amount of at least 2 parts by weight, in which case it has the advantage of maintaining a balance between physical properties and improving mechanical properties. Although linear alcohols are known to have excellent effects in theory, the present invention has obtained results that are different from such theoretical results, and it has been confirmed that a more balanced physical property is obtained when an isomer mixture containing a branched alcohol is applied.

[0052] In addition, the isomer mixture of hexyl alcohol can include 1-hexanol, 2-methylpentanol, 3-methylpentanol and cyclopentylmethanol.Preferably, the isomer mixture further includes cyclopentylmethanol, which maintains a balance between the physical properties and slightly improves the mechanical properties and plasticization efficiency.

[0053] In this case, the cyclopentylmethanol may be present in an amount of 20 parts by weight or less, preferably 15 parts by weight or less, based on 100 parts by weight of the isomer mixture, and may be absent or the minimum amount for obtaining the effect thereof may be 2 parts by weight.

[0054] Specifically, depending on the ratio of branched alkyl groups to the total alkyl groups in the final composition, and further, the ratio of a specific branched alkyl group among the branched alkyl groups, it is possible to achieve a balance between the physical properties of plasticization efficiency and migration / weight loss characteristics, and to maintain the same or higher levels of mechanical properties such as tensile strength and elongation, and stress resistance, which can be achieved by the components of the above-mentioned hexyl alcohol isomers and their component ratios.

[0055] This makes it possible to eliminate the environmental problems associated with existing phthalate-based products and realize products with improved weight loss properties; it also makes it possible to significantly improve the migration and weight loss properties of existing terephthalate-based products, and realize products with significantly improved light resistance compared to existing commercial products.

[0056] The method for producing the plasticizer composition according to one embodiment of the present invention is a method well known in the art and can be applied without any particular limitation as long as it can produce the above-mentioned plasticizer composition.

[0057] For example, the composition can be prepared by directly esterifying an isomeric mixture of 1,2,3-propanetricarboxylic acid, its anhydride or derivative with hexyl alcohol, or by transesterifying an isomeric mixture of trialkyl 1,2,3-propanetricarboxylate with hexyl alcohol.

[0058] The plasticizer composition according to one embodiment of the present invention is a material prepared by appropriately carrying out the esterification reaction. As long as the above-mentioned conditions are met, such as the weight ratio between the tricarboxylates of each system, the preparation method is not particularly limited.

[0059] For example, the direct esterification reaction can be carried out by introducing an isomer mixture of 1,2,3-propanetricarboxylic acid or a derivative thereof and hexyl alcohol, adding a catalyst, and reacting under a nitrogen atmosphere, removing unreacted raw materials, neutralizing (or deactivating) the unreacted raw materials and the catalyst, and removing impurities (e.g., distillation under reduced pressure) and filtering.

[0060] The components and weight ratios of the isomer mixture of hexyl alcohol are as described above. The isomer mixture of hexyl alcohol can be used in a range of 200-900 mol%, 200-700 mol%, 200-600 mol%, 250-600 mol%, or 270-600 mol% relative to 100 mol% of the acid, and the component ratio in the final composition can be controlled by controlling the content of this alcohol.

[0061] 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, the catalyst may be tetraalkyl titanate. Preferably, paratoluenesulfonic acid, methanesulfonic acid, and the like are suitable as acid catalysts with low activation temperatures.

[0062] The amount of catalyst used may vary depending on the type. For example, in the case of a homogeneous catalyst, the amount may be within the range of 0.01 to 5 wt%, 0.01 to 3 wt%, 1 to 5 wt%, or 2 to 4 wt%, relative to 100 wt% of the total amount of reactants. In the case of a heterogeneous catalyst, the amount may be within the range of 5 to 200 wt%, 5 to 100 wt%, 20 to 200 wt%, or 20 to 150 wt% of the total amount of reactants.

[0063] In this case, the reaction temperature can be within the range of 100 to 280°C, 100 to 250°C, or 120 to 230°C.

[0064] As another example, the transesterification reaction may be a reaction between a trialkyl 1,2,3-propane tricarboxylate and an isomer mixture of hexyl alcohol. In order to minimize impurities, the alkyl group of the trialkyl 1,2,3-propane tricarboxylate is preferably a hexyl group, and in this case, when the hexyl group of the tricarboxylate is linear, the isomer mixture of hexyl alcohol contains a branched alcohol, or when the hexyl group of the tricarboxylate is branched, the isomer mixture of hexyl alcohol contains a linear alcohol, so that the alkyl group of the finally obtained 1,2,3-propane tricarboxylate may contain both linear and branched alkyl groups.

[0065] The term "transesterification reaction" as used herein means a reaction in which an alcohol reacts with an ester, and R" of the ester is interchanged with R' of the alcohol, as shown in the following reaction scheme 1.

[0066] [ka]

[0067] Generally, when the transesterification reaction is carried out, four types of ester compositions can be produced depending on the number of four cases, such as when there are two types of alkyl groups, when the alkoxide of the alcohol attacks the carbons of three ester (RCOOR'') groups present in the ester compound; when it attacks the carbons of two ester (RCOOR'') groups present in the ester compound; when it attacks the carbon of one ester (RCOOR'') group present in the ester compound; and when it is unreacted and no reaction has occurred.

[0068] However, in the case of the tricarboxylates contained in the plasticizer composition according to the present invention, three types can be formed in each case where two ester groups are exchanged and one ester group is exchanged depending on the bonding position of the ester group, so that up to eight types of compounds can be mixed in the final composition. However, in the case of the isomeric mixture of hexyl alcohol according to the present invention, the alkyl groups present are two or more types, so the types can be more diverse.

[0069] Moreover, the transesterification reaction has an advantage over the esterification reaction between an acid and an alcohol in that it does not cause a wastewater problem.

[0070] The mixture produced by the transesterification reaction can control the composition ratio of the mixture according to the amount of alcohol added. The amount of alcohol added can be 0.1 to 200 parts by weight, specifically 1 to 150 parts by weight, and more specifically 5 to 100 parts by weight, based on 100 parts by weight of the trialkyl 1,2,3-propane tricarboxylate compound. For reference, the component ratio in the final composition can be determined by the amount of alcohol added, as in the direct esterification reaction.

[0071] According to one embodiment of the present invention, the transesterification reaction is carried out at a reaction temperature of 120 to 190°C, preferably 135 to 180°C, and more preferably 141 to 179°C, for 10 minutes to 10 hours, preferably 30 minutes to 8 hours, and more preferably 1 to 6 hours. Within the above temperature and time ranges, the component ratio of the final plasticizer composition can be efficiently controlled. In this case, the reaction time can be calculated from the time when the reactants reach the reaction temperature after heating.

[0072] The transesterification reaction can be carried out in the presence of an acid catalyst or a metal catalyst, which has the effect of shortening the reaction time.

[0073] The acid catalyst may be, for example, sulfuric acid, methanesulfonic acid, or p-toluenesulfonic acid, and the metal catalyst may be, for example, an organometallic catalyst, a metal oxide catalyst, a metal salt catalyst, or a metal itself.

[0074] The metal component may be, for example, any one selected from the group consisting of tin, titanium, and zirconium, or a mixture of two or more of these.

[0075] In addition, the method may further include a step of distilling and removing unreacted alcohol and reaction by-products after the transesterification reaction. As an example, the distillation may be a two-step distillation in which the alcohol and reaction by-products are separated using the difference in boiling points. As another example, the distillation may be a mixed distillation. In this case, the ester-based plasticizer composition can be relatively stably obtained at a desired composition ratio. The mixed distillation means that the unreacted alcohol and reaction by-products are distilled simultaneously.

[0076] According to another embodiment of the present invention, there is provided a resin composition comprising the above-described plasticizer composition and a resin.

[0077] The resin may be any resin known in the art, including, 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, polylactic acid, natural rubber, synthetic rubber, and thermoplastic elastomer.

[0078] The plasticizer composition can be contained 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.

[0079] Generally, the resin in which the plasticizer composition is used can be manufactured as a resin product by melt processing or plastisol processing, and melt-processed resins and plastisol-processed resins can be produced differently depending on the polymerization method.

[0080] 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; such vinyl chloride polymer is called straight vinyl chloride polymer, whereas when it is used in plastisol processing, it is produced by emulsion polymerization or the like and a resin in a sol state as fine resin particles is used; such vinyl chloride polymer is called paste vinyl chloride resin.

[0081] 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.

[0082] The resin composition may further contain a filler, the amount of the filler being 0 to 300 parts by weight, preferably 50 to 200 parts by weight, and more preferably 100 to 200 parts by weight, relative to 100 parts by weight of the resin.

[0083] The filler can be any filler known in the art, and is not particularly limited.For example, it can be one or more mixtures selected from silica, magnesium carbonate, calcium carbonate, hard carbon, talc, magnesium hydroxide, titanium dioxide, magnesium oxide, potassium hydroxide, aluminum hydroxide, aluminum silicate, magnesium silicate, and barium sulfate.

[0084] Furthermore, the resin composition may further contain other additives such as a stabilizer, if necessary. The amount of each of the other additives such as the stabilizer may be, for example, 0 to 20 parts by weight, preferably 1 to 15 parts by weight, relative to 100 parts by weight of the resin.

[0085] 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.

[0086] As described above, the resin composition can be applied to both melt processing and plastisol processing. For example, the melt processing can be a calendaring process, an extrusion process, or an injection process, and the plastisol processing can be a coating process.

[0087] Working Example Hereinafter, the present invention will be described in detail with reference to examples in order to specifically explain the present invention. However, the examples according to the present invention can be modified into various other 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.

[0088] Example 1 299.4 g of 1,2,3-propanetricarboxylic acid, 781.7 g of a mixture of hexyl alcohol isomers, and 0.9 g of tetrabutyl titanate (TnBT) were added to a reactor equipped with an agitator, a condenser, and a decanter, and then an esterification reaction was carried out under a nitrogen atmosphere to terminate the reaction. The catalyst and the product were neutralized with an alkaline aqueous solution, and the unreacted alcohol and water were purified to finally obtain a plasticizer composition.

[0089] The alcohol composition of the hexyl alcohol isomer mixture used here was a mixture of 1-hexanol, 2-methylpentanol, 3-methylpentanol and cyclopentylmethanol in a weight ratio of 10:40:45:5.

[0090] Example 2 The same procedure as in Example 1 was repeated, but a plasticizer composition was obtained using a mixture of 1-hexanol, 2-methylpentanol, and 3-methylpentanol in a weight ratio of 20:35:45 as the mixture of isomers of hexyl alcohol.

[0091] Example 3 The same procedure as in Example 1 was repeated, but a plasticizer composition was obtained using a mixture of hexyl alcohol isomers in which 1-hexanol, 2-methylpentanol, 3-methylpentanol, and cyclopentylmethanol were mixed in a weight ratio of 10:45:30:15.

[0092] Comparative Example 1 Dioctyl phthalate (DOP, manufactured by LG Chemical) was used as a plasticizer.

[0093] Comparative Example 2 Diisononyl phthalate (DINP, manufactured by LG Chem) was used as a plasticizer.

[0094] Comparative Example 3 Di(2-ethylhexyl) terephthalate (GL300, manufactured by LG Chemical) was used as a plasticizer.

[0095] Comparative Example 4 A composition containing dibutyl terephthalate (DBTP), butyl (2-ethylhexyl) terephthalate (BEHTP) and di(2-ethylhexyl) terephthalate (DEHTP) at 6.3 wt%, 38.8 wt% and 54.9 wt%, respectively (GL500, LG Chem) was used as a plasticizer.

[0096] Comparative Example 5 A plasticizer composition was obtained in the same manner as in Example 1, except that 326.4 g of citric acid was used instead of 1,2,3-propanetricarboxylic acid.

[0097] Comparative Example 6 A plasticizer composition was obtained in the same manner as in Comparative Example 5, except that acetic anhydride was added after the esterification reaction to perform acetylation.

[0098] Comparative Example 7 A plasticizer composition was obtained in the same manner as in Example 1, except that 781.7 g of 2-methylpentanol alone was used instead of the isomer mixture of hexyl alcohol.

[0099] Comparative Example 8 A plasticizer composition was obtained in the same manner as in Example 1, except that 680 g of n-pentanol alone was used instead of the isomer mixture of hexyl alcohol.

[0100] Comparative Example 9 A plasticizer composition was obtained in the same manner as in Example 1, except that 890 g of n-heptanol alone was used instead of the isomer mixture of hexyl alcohol.

[0101] The types of acids and alcohols used in the above examples and comparative examples are summarized in Table 1 below.

[0102] [Table 1]

[0103] 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.

[0104] (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)

[0105] (2) Mixing: Mix at 98℃ and 700 rpm

[0106] (3) Preparation of test pieces: 1T, 2T and 3T sheets were prepared by working 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).

[0107] (4) Evaluation items 1)Hardness In accordance with ASTM D2240, Shore hardness (Shore "A" and "D") at 25°C was measured for 10 seconds using a 3T test piece. The smaller the value, the better the plasticization efficiency.

[0108] 2) Tensile strength and tensile strength retention According to the method of ASTM D638, the test equipment UTM (manufacturer: Instron, model: 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 as follows:

[0109] Tensile strength (kgf / cm 2 ) = Load value (kgf) / thickness (cm) x width (cm)

[0110] The tensile retention rate was measured by measuring the ratio of the tensile strength remaining in a test piece after leaving the test piece in an oven at 100° C. for 168 hours, and the measurement method was the same as the above-mentioned method for measuring tensile strength.

[0111] 3) Measurement of tensile elongation and tensile elongation retentionAccording to the method of ASTM D638, 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 the elongation was calculated as follows:

[0112] The elongation rate (%) was calculated as follows: length after elongation / initial length×100.

[0113] The residual elongation rate was measured by measuring the ratio of the elongation rate remaining in the test piece after leaving the test piece in an oven at 100° C. for 168 hours, and the measurement method was the same as the above-mentioned method for measuring the elongation rate.

[0114] 4) Measurement of migration loss : According to KSM-3156, a test piece with a thickness of 2 mm or more was obtained, and a glass plate was attached to both sides of the 1T test piece, and then a load of 1 kgf / cm2 was applied. The test piece was left in a hot air circulating oven (80°C) for 72 hours, then removed and cooled at room temperature for 4 hours. After that, the glass plates attached to both sides of the test piece were removed, and the weights of the glass plates and the specimen plate before and after leaving them in the oven were measured, and the amount of migration loss was calculated using the following formula. Migration loss (%) = {(initial weight of test piece at room temperature - weight of test piece after leaving in oven) / (initial weight of test piece at room temperature)} x 100

[0115] 5) Measurement of volatile loss The test piece thus prepared was subjected to a test at 80° C. for 72 hours, and then the weight of the test piece was measured.

[0116] Heat loss (wt%)=initial test piece weight−(test piece weight after 72 hours at 80° C.) / initial test piece weight×100.

[0117] 6) Stress test (stress resistance) A 2mm thick test piece was left in a folded state at 23℃ for 168 hours, after which the degree of migration (exudation) was observed and the results were recorded as a number. The closer to 0, the better the properties.

[0118] (5) Evaluation results The evaluation results for the above items are shown in Tables 2 and 3 below.

[0119] [Table 2]

[0120] [Table 3]

[0121] Referring to Tables 2 and 3, it can be seen that in the case of Examples 1 to 3 in which the plasticizer composition according to one embodiment of the present invention is applied, the migration loss, heat loss, and stress resistance are similar to those of Comparative Examples 1 and 2, which are used as existing phthalate-based products, and the plasticization efficiency and elongation are improved. Comparative Examples 1 and 2 are existing products that show excellent performance but are phthalate-based and have the problem of being environmentally unfriendly, and the above results suggest that the plasticizer composition of the present invention, which does not contain phthalate and is environmentally friendly, can fully replace the existing products.

[0122] In addition, Comparative Examples 3 and 4 are environmentally friendly products and are used in place of Comparative Examples 1 and 2. However, they have problems in that their migration properties and stress resistance are significantly inferior to existing products and Examples 1 to 3 of the present invention, and they are also inferior to Examples 1 to 3 of the present invention in terms of plasticization efficiency.

[0123] In Comparative Examples 5 and 6, a mixture of isomers of hexyl alcohol was used in the same manner as in Examples 1 to 3 of the present invention, except that citric acid or acetylcitric acid was used instead of 1,2,3-propanetricarboxylic acid. Comparative Example 5, in which citric acid was used, was inferior to Examples 1 to 3 in terms of plasticization efficiency, tensile properties, and elongation properties, while Comparative Example 6, in which citric acid was used and acetylation was further performed, was inferior to Examples 1 to 3 in terms of plasticization efficiency, elongation properties, migration resistance, and stress resistance.

[0124] In addition, in Comparative Example 7, in which 1,2,3-propanetricarboxylic acid is used as in the examples of the present invention, but a single compound of 2-methylpentanol is used as the alcohol, instead of a mixture of isomers of hexyl alcohol, the tensile properties and elongation properties are inferior to those of Examples 1 to 3. In Comparative Example 8, in which 1,2,3-propanetricarboxylic acid is used as in the examples of the present invention, but n-pentanol having a carbon number of 5 is used as the alcohol, the tensile properties and elongation properties are also significantly inferior to those of Examples 1 to 3, and the heat loss and stress resistance are also inferior to those of Examples 1 to 3. Finally, in Comparative Example 9, in which n-heptanol, an alcohol having a carbon number of 7, is used, the plasticization efficiency, tensile properties, elongation properties, migration resistance, and stress resistance are inferior to those of Examples 1 to 3.

[0125] As a result, when an esterification reaction product of an isomer mixture of 1,2,3-propanetricarboxylic acid and hexyl alcohol is used as a plasticizer as in the examples of the present invention, a plasticizer that can fully replace existing products and exhibits excellent performance can be realized. In particular, in the present invention, it has been confirmed that a plasticizer composition having an excellent balance between various physical properties and excellent physical properties can be provided by selecting and applying an acid and an alcohol, i.e., an isomer mixture of 1,2,3-propanetricarboxylic acid and hexyl alcohol, as the acid and the alcohol.

Claims

1. The propane tricarboxylate-based composition includes one or more propane tricarboxylates represented by the following formula 1: the alkyl group of the propane tricarboxylate is derived from an isomeric mixture of hexyl alcohol; a tricarboxylate-based plasticizer composition, the isomer mixture of hexyl alcohol including two or more selected from the group consisting of 1-hexanol, 1-methylpentanol, 2-methylpentanol, 3-methylpentanol, 4-methylpentanol, 1,1-dimethylbutanol, 1,2-dimethylbutanol, 1,3-dimethylbutanol, 2,2-dimethylbutanol, 2,3-dimethylbutanol, 3,3-dimethylbutanol, 1-ethylbutanol, 2-ethylbutanol, 3-ethylbutanol, and cyclopentylmethanol, and the isomer mixture of hexyl alcohol has a degree of branching of 1.5 or less. 【Chemistry 1】 In the above Chemical Formula 1, R １ ~R ３ are each independently an n-hexyl group, a branched hexyl group, or a cyclopentylmethyl group.

2. 2. The plasticizer composition of claim 1, wherein the isomeric mixture of hexyl alcohols comprises 1-hexanol, 2-methylpentanol, and 3-methylpentanol.

3. 2. The plasticizer composition according to claim 1, wherein the isomer mixture of hexyl alcohol contains 40 parts by weight or more of a branched alcohol per 100 parts by weight of the isomer mixture.

4. 2. The plasticizer composition according to claim 1, wherein the isomer mixture of hexyl alcohol contains 50 to 95 parts by weight of a branched alcohol per 100 parts by weight of the isomer mixture.

5. 2. The plasticizer composition according to claim 1, wherein the isomer mixture of hexyl alcohol contains 40 parts by weight or less of 1-hexanol per 100 parts by weight of the isomer mixture.

6. 2. The plasticizer composition of claim 1, wherein the isomeric mixture of hexyl alcohols comprises 1-hexanol, 2-methylpentanol, 3-methylpentanol, and cyclopentylmethanol.

7. The plasticizer composition according to claim 6, wherein the isomer mixture of hexyl alcohol contains 20 parts by weight or less of cyclopentylmethanol per 100 parts by weight of the isomer mixture.

8. A resin composition comprising 100 parts by weight of a resin and 5 to 150 parts by weight of the plasticizer composition of claim 1.

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, polylactic acid, natural rubber, and synthetic rubber.

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