Aconitate plasticizer composition and resin composition containing the same

Abstract

The present invention is characterized in that the alkyl group thereof is derived from aconitate of an isomer mixture of hexanol, and when applied to resin, excellent migration resistance, volatilization loss and stress resistance as well as high plasticizing efficiency can be obtained.

Description

Technical Field

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

[0002] Generally, in the case of plasticizers, alcohols react with polycarboxylic acids such as phthalic acid and adipic acid to form esters corresponding thereto. In addition, in view of domestic and foreign regulations restricting phthalate plasticizers that are harmful to the human body, research on plasticizer compositions that can replace phthalate plasticizers, such as terephthalate plasticizers, adipate plasticizers, and other polymer plasticizers has been continuing.

[0003] At the same time, there is an increasing demand for environmentally friendly products in the plastisol industry, calendaring industry and extrusion / injection compounding industry, such as flooring, wallpaper, soft and hard sheets, and in order to improve the quality characteristics, processability and productivity of each final product, it is necessary to use suitable plasticizers while considering factors such as discoloration, migration properties and mechanical properties.

[0004] Supplementary materials such as plasticizers, fillers, stabilizers, viscosity reducers, dispersants, defoamers and blowing agents are mixed with PVC resins according to the properties required in the industry in different fields of use, such as tensile strength, elongation, light resistance, migration properties, gelling properties or absorption rate.

[0005] For example, in the plasticizer combination suitable for PVC, when the most commonly used di(2-ethylhexyl) terephthalate with relatively low cost is applied, the hardness or sol viscosity is high, the absorption speed of the plasticizer is relatively slow, and the migration performance and stress migration performance are poor.

[0006] In order to overcome the above limitations, as a composition containing DEHTP, the product obtained by ester exchange with butanol can be considered as a plasticizer. In this case, the use of the product can improve the plasticizing efficiency, but it will lead to volatilization loss or poor thermal stability, a slight decrease in mechanical properties, and the need to improve physical properties. Therefore, in addition to generally using a secondary plasticizer together to make up for the shortcomings, there is currently no other solution.

[0007] However, the use of secondary plasticizers brings with it the following unexpected drawbacks: changes in physical properties are difficult to predict, the unit cost of the product may increase, the improvement in physical properties is not significant except in certain cases, and compatibility with the resin may be problematic.

[0008] In addition, when trimellitic acid ester materials, such as tri(2-ethylhexyl) trimellitic acid ester or triisononyl trimellitic acid ester, are used to improve the poor migration and loss properties of DEHTP products, the migration or loss properties may be improved, but the plasticizing efficiency may decrease, and a considerable amount of material needs to be added to provide a resin with appropriate plasticizing properties, and the relatively high unit price of the product makes it impossible to sell the product on the market.

[0009] Therefore, it is necessary to develop a product for solving the environmental problems caused by phthalate products which are commonly used products, or to develop a product that corrects the bad physical properties of environmentally friendly products to solve the environmental problems of phthalate products. Summary of the invention

[0010] Technical issues

[0011] One aspect of the present invention provides a plasticizer composition capable of improving plasticizing efficiency and mobility and also maintaining mechanical properties and stress resistance at least at the same level as conventional plasticizers by comprising an aconitate ester in which the alkyl group is derived from an isomeric mixture of hexanol.

[0012] Technical Solution

[0013] In order to cope with the above-mentioned task, the present invention provides a plasticizer composition and a resin composition comprising the plasticizer composition.

[0014] (1) According to one aspect of the present invention, there is provided an aconitate plasticizer composition, which comprises an aconitate composition containing at least one aconitate of the following formula 1:

[0015] The alkyl group of the aconitate is derived from an isomeric mixture of hexanol, and

[0016] The isomeric mixture of hexanol 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,

[0017] [Formula 1]

[0018]

[0019] In the above formula 1,

[0020] R 1 To R 3 Each is independently n-hexyl, branched hexyl or cyclopentylmethyl.

[0021] (2) The present invention provides the plasticizer composition as described in (1) above, wherein the degree of branching of the isomer mixture of hexanol is 2.0 or less.

[0022] (3) The present invention provides the plasticizer composition as described in (1) or (2) above, wherein the degree of branching of the isomer mixture of hexanol is 1.5 or less.

[0023] (4) The present invention provides the plasticizer composition as described in any one of (1) to (3) above, wherein the isomer mixture of hexanol comprises 1-hexanol, 2-methylpentanol and 3-methylpentanol.

[0024] (5) The present invention provides the plasticizer composition as described in any one of (1) to (4) above, wherein the isomer mixture of hexanol contains 40 parts by weight or more of branched alcohols relative to 100 parts by weight of the isomer mixture of hexanol.

[0025] (6) The present invention provides a plasticizer composition as described in any one of (1) to (5) above, wherein the isomer mixture of hexanol contains 50 to 95 parts by weight of branched alcohol relative to 100 parts by weight of the isomer mixture of hexanol.

[0026] (7) The present invention provides the plasticizer composition as described in any one of (1) to (6) above, wherein the isomer mixture of hexanol contains 40 parts by weight or less of 1-hexanol relative to 100 parts by weight of the isomer mixture of hexanol.

[0027] (8) The present invention provides the plasticizer composition as described in any one of (1) to (7) above, wherein the isomer mixture of hexanol comprises 1-hexanol, 2-methylpentanol, 3-methylpentanol and cyclopentylmethanol.

[0028] (9) The present invention provides the plasticizer composition as described in any one of (1) to (8) above, wherein the isomer mixture of hexanol contains 20 parts by weight or less of cyclopentylmethanol relative to 100 parts by weight of the isomer mixture of hexanol.

[0029] (10) According to another aspect of the present invention, there is provided a resin composition comprising:

[0030] 100 parts by weight of a resin; and 5 to 150 parts by weight of the plasticizer composition described in any one of (1) to (9) above.

[0031] (11) The present invention provides a resin composition as described in (10) above, wherein the resin is one or more selected from the group consisting of a linear vinyl chloride polymer, a paste vinyl chloride polymer, an ethylene-vinyl acetate copolymer, an ethylene polymer, a propylene polymer, a polyketone, a polystyrene, a polyurethane, a polylactic acid, a natural rubber and a synthetic rubber.

[0032] Beneficial Effects

[0033] When the plasticizer composition according to an embodiment of the present invention is used in a resin composition, mechanical properties and stress resistance can be maintained and improved, at least to the same level as conventional plasticizers, and properties such as migration resistance and plasticization efficiency can also be improved. DETAILED DESCRIPTION

[0034] It should be understood that the words or terms used in the specification and claims of the present invention should not be interpreted as being limited to the meanings defined in common dictionaries. It will be further understood that these words or terms should be interpreted as having meanings consistent with their meanings in the relevant technical background and the technical concept of the present invention, based on the principle that the inventor can appropriately define the meanings of these words or terms to best explain the present invention.

[0035] Definition of terms

[0036] As used herein, the term "composition" encompasses compositions comprising a mixture of materials, as well as reaction products and decomposition products formed from the materials of the composition.

[0037] As used herein, the term "linear vinyl chloride polymer" is a vinyl chloride polymer that is polymerized by suspension polymerization or bulk polymerization, and refers to a polymer in the form of porous particles in which a large number of pores with a size of tens to hundreds of microns are distributed, with no cohesive force and good fluidity.

[0038] As used herein, the term "paste vinyl chloride polymer" is a vinyl chloride polymer that is polymerized by microsuspension polymerization, microseed polymerization or emulsion polymerization, and refers to a polymer in the form of fine, compact, non-porous particles with a size of tens to thousands of nanometers, cohesiveness and poor fluidity.

[0039] The terms "comprising" and "having" and their derivatives are not meant to exclude the presence of any additional ingredients, steps or procedures, whether or not they are specifically disclosed. To avoid any uncertainty, all compositions claimed through the use of the term "comprising", whether polymeric or otherwise, may include any additional additives, adjuvants or compounds unless otherwise specified. Conversely, the term "consisting essentially of excludes any other ingredients, steps or procedures from the scope of any subsequent description and excludes those ingredients that are not essential to operability. The term "consisting of excludes any ingredient, step or procedure not specifically described or listed.

[0040] Measurement method

[0041] In the specification, the analysis was performed by gas chromatography using a gas chromatograph (Agilent 7890GC, manufactured by Agilent Technologies Inc., column: HP-5, carrier gas: helium (flow rate 2.4 mL / min), detector: FID, injection volume: 1 μL, initial value: 70°C / 4.2 minutes, final value: 280°C / 7.8 minutes, program rate: 15°C / min).

[0042] In this specification, "hardness" refers to the Shore hardness (Shore "A" and / or Shore "D") measured at 25°C according to ASTM D2240. Hardness is measured under the condition of 3T 10s and can be used as an index for evaluating plasticization efficiency. Low hardness indicates excellent plasticization efficiency.

[0043] In the specification, "tensile strength" is measured according to ASTM D638 as follows: A 1T specimen is pulled at a crosshead speed of 200 mm / min using a universal testing machine (UTM; 4466 manufactured by Instron), and then the point at which the specimen breaks is determined and substituted into the following equation 1.

[0044] [Equation 1]

[0045] Tensile strength (kgf / cm 2 ) = load value (kgf) / thickness (cm) × width (cm)

[0046] In this specification, "elongation" is measured according to ASTM D638 as follows: A 1T specimen is pulled at a crosshead speed of 200 mm / min using UTM, and then the time point at which the specimen breaks is determined and substituted into the following Equation 2.

[0047] [Equation 2]

[0048] Elongation (%) = elongated length / initial length × 100

[0049] In this specification, "migration loss" is measured as follows in accordance with the provisions of KSM-3156. Prepare a sample with a thickness of 2 mm or more, attach glass plates to both sides of the sample, and then apply 1 kgf / cm 2 The sample was placed in a hot air convection oven (80°C) for 72 hours, then removed from the oven and cooled at room temperature for 4 hours. After that, the glass plates attached to both sides of the sample were removed, and the weight of the sample and the glass plates before and after being placed in the oven was measured to determine the migration loss using the following equation 3.

[0050] [Equation 3]

[0051] Migration loss (%) = {(initial weight of sample - weight of sample after taking out of oven) / initial weight of sample} × 100

[0052] In the specification, "volatile loss" is measured by treating a sample at 80°C for 72 hours and then weighing the sample.

[0053] [Equation 4]

[0054] Volatilization loss (wt%) = {(initial weight of sample - weight of sample after treatment) / initial weight of sample} × 100

[0055] In the case of the above-mentioned various measurement methods, detailed conditions such as temperature, rotation speed, time, etc. may slightly change in some cases, and when the detailed conditions change, the measurement method and conditions are specified separately.

[0056] Hereinafter, the present invention will be described in detail to help understanding of the present invention.

[0057] According to an embodiment of the present invention, an aconitate plasticizer composition is provided, comprising an aconitate composition containing at least one aconitate of the following formula 1, wherein the alkyl group of the aconitate is derived from an isomeric mixture of hexanol, and the isomeric mixture of hexanol comprises two or more selected from 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.

[0058] [Formula 1]

[0059]

[0060] In the above formula 1,

[0061] R 1 To R 3 Each is independently n-hexyl, branched hexyl or cyclopentylmethyl.

[0062] The plasticizer composition may be a product produced by direct esterification between aconitic acid or its derivatives and a hexanol mixture, or by transesterification between aconitic acid trialkyl esters and a hexanol mixture, in which case the hexanol mixture used may be a hexanol mixture with different structures, i.e., a mixture of structural isomers. More specifically, the isomer mixture of hexanol 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.

[0063] R in the above formula 1 1 To R 3 The alkyl group of can be determined according to the alcohol contained in such hexanol isomers, and in the final composition, a diverse composition of three, two or one hexanol isomer alkyl groups combined with three alkyl groups can be contained, and the component ratio in the final composition can be determined by the ratio of the respective structural isomer components in the hexanol mixture subjected to the reaction.

[0064] As described above, with respect to the application of aconitate plasticizers, when an alcohol having 6 carbon atoms is used, the tensile strength, elongation and volatility loss may be significantly improved compared to an alcohol having less than 6 carbon atoms, and excellent plasticizing efficiency, migration resistance, tensile strength and elongation may be achieved compared to an alcohol having more than 6 carbon atoms.

[0065] The degree of branching of the hexanol isomer mixture of the plasticizer composition according to an embodiment of the present invention is less than 2.0, preferably less than 1.5. Specifically, the degree of branching can be less than 1.5, less than 1.3, more preferably less than 1.1, particularly preferably less than 1.0. In addition, the degree of branching can be more than 0.1, more than 0.2, more than 0.3, most preferably more than 0.7. In the aconitate plasticizer composition produced with hexanol, the degree of branching of the hexanol isomer mixture can also remain unchanged. When the degree of branching is too high, the balance between the physical properties may be broken, so that the product cannot meet any one or more evaluation criteria, but in the preferred range of less than 1.5, the improvement of migration loss and volatilization loss and mechanical properties can be further optimized, and a good balance between the physical properties can be obtained.

[0066] In this case, the degree of branching may represent the number of branched carbons of the alkyl group combined with the material contained in the composition, and may be determined according to the weight ratio of the corresponding materials. For example, when the alcohol mixture comprises 60% by weight of n-hexanol, 30% by weight of methylpentanol, and 10% by weight of ethylbutanol, the number of branched carbons of each alcohol is 0, 1, and 2, and the degree of branching may be determined as 0.5 according to [(60×0)+(30×1)+(10×2)] / 100. Meanwhile, with regard to the definition of the degree of branching in the present invention, the number of branched carbons of cyclopentylmethanol is considered to be 0.

[0067] The isomeric mixture of n-hexanol may contain 1-hexanol and 2-methylpentanol. Therefore, when 1-hexanol and 2-methylpentanol are included together, a balance between physical properties can be maintained and a good effect can be achieved in terms of volatility loss. Preferably, the isomeric mixture of hexanol may further contain 3-methylpentanol, in which case the balance between physical properties is considerable.

[0068] Relative to 100 parts by weight of the isomer mixture, the content of the branched hexanol including 2-methylpentanol can be 40 parts by weight or more, 50 parts by weight or more, 60 parts by weight or more, preferably 65 parts by weight or more, 70 parts by weight or more. The content of the branched hexanol including 2-methylpentanol can be 100 parts by weight or less, 99 parts by weight or less, 98 parts by weight or less, preferably 95 parts by weight or less, or 90 parts by weight or less. When the branched hexanol is included within this range, improvement in mechanical properties can be expected.

[0069] In addition, the content of the straight-chain alcohol of 1-hexanol can be 50 weight parts or less, 40 weight parts or less, preferably 30 weight parts or less, relative to 100 weight parts of the isomer mixture. 1-hexanol may not be present in the composition, but the content can be at least 2 weight parts or more, and in this case, the balance between the physical properties can be maintained and improved mechanical properties can also be achieved. In theory, it is known that straight-chain alcohols show excellent properties, but in the present invention, different results are obtained, confirming that even better balance between physical properties can be obtained using isomer mixtures containing branched alcohols.

[0070] Furthermore, the isomer mixture of hexanol may contain 1-hexanol, 2-methylpentanol, 3-methylpentanol and cyclopentylmethanol. The plasticizing efficiency or the tensile strength may preferably be slightly improved by further containing cyclopentylmethanol.

[0071] In this case, the content of cyclopentylmethanol may be 20 parts by weight or less, preferably 15 parts by weight or less, or absent, or at least 2 parts by weight relative to 100 parts by weight of the isomer mixture, thereby obtaining the effect.

[0072] Specifically, according to the ratio of the branched alkyl group in the total alkyl group in the final composition, and further, according to the ratio of the specific branched alkyl group in the branched alkyl group, the balance between the plasticizing efficiency and the physical properties, such as the migration / loss property, can be controlled, and the mechanical properties, such as the tensile strength and the elongation, and the stress resistance can be maintained at least at the same level, which can be achieved from the above-mentioned components of the hexanol isomers and the component ratio thereof.

[0073] Through the above-mentioned methods, it is possible to achieve products that prevent the environmental problems of commonly used phthalate products and further improve the loss performance, significantly improve the migration and plasticization efficiency of commonly used terephthalate products, and achieve products with improved volatile loss compared to common products on the market.

[0074] As a method of preparing the plasticizer composition according to an embodiment of the present invention, any method of preparing the above-mentioned plasticizer composition known in the art may be applied without particular limitation.

[0075] For example, the composition can be prepared by direct esterification between aconitic acid or its anhydride and an isomeric mixture of hexanol, or by transesterification between trihexyl aconitate and an isomeric mixture of hexanol.

[0076] The plasticizer composition according to an embodiment of the present invention is a material prepared by appropriately performing esterification, and the preparation method thereof is not particularly limited as long as the above conditions are satisfied and the weight ratio between the aconitic acid esters of each family is appropriately adjusted.

[0077] For example, direct esterification can be carried out in the following manner: injecting a mixture of isomers of aconitic acid or its derivatives and hexanol, then adding a catalyst, inducing the reaction in a nitrogen environment; removing unreacted starting materials; neutralizing (or deactivating) unreacted starting materials and catalyst; and removing (e.g., using reduced pressure distillation) and filtering impurities.

[0078] The components of the isomeric mixture of hexanol and the weight ratio of each component are the same as above. The isomeric mixture of hexanol can be used in the range of 200 mol% to 900 mol%, 200 mol% to 700 mol%, 200 mol% to 600 mol%, 250 mol% to 600 mol% or 270 to 600 mol% relative to 100 mol% of the acid, and the ratio of the components in the final composition can be controlled by controlling the amount of alcohol.

[0079] The catalyst can be, for example, selected from acid catalysts such as sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid, p-toluenesulfonic acid, methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid and alkyl sulfate, metal salts such as aluminum lactate, lithium fluoride, potassium chloride, cesium chloride, calcium chloride, ferric chloride and aluminum phosphate, metal oxides such as heteropolyacids, natural / synthetic zeolites, cation and anion exchange resins, and organic metals such as tetraalkyl titanates and polymers thereof One or more. Specifically, the catalyst can use, for example, tetraalkyl titanates. Preferably, p-toluenesulfonic acid, methanesulfonic acid, etc. may be suitable as acidic catalysts with low activation temperature.

[0080] The amount of the catalyst used may vary depending on its type, for example, the amount of a homogeneous catalyst used may be 0.01 wt% to 5 wt%, 0.01 wt% to 3 wt%, 1 wt% to 5 wt%, or 2 wt% to 4 wt%, relative to 100 wt% of the total amount of reactants; the amount of a heterogeneous catalyst used may be 5 wt% to 200 wt%, 5 wt% to 100 wt%, 20 wt% to 200 wt%, or 20 wt% to 150 wt%, relative to the total amount of reactants.

[0081] In this case, the reaction temperature may be in the range of 100 to 280°C, 100 to 250°C, or 120 to 230°C.

[0082] In another example, the transesterification may be a reaction between trialkyl aconitate and an isomeric mixture of hexanol. In terms of minimizing impurities, the alkyl group of the trialkyl aconitate may preferably be a hexyl group, in which case, when the hexyl group of the trialkyl aconitate is linear, the isomeric mixture of hexanol is set to contain branched alcohols, or when the hexyl group of the trialkyl aconitate is branched, the isomeric mixture of hexanol is set to contain linear alcohols, so that the alkyl group of the aconitate finally obtained may contain both linear and branched types.

[0083] As used herein, "ester exchange" refers to the reaction between an alcohol and an ester as shown in the following reaction formula 1, whereby the R" of the ester is exchanged with the R' of the alcohol:

[0084] [Reaction formula 1]

[0085]

[0086] Generally speaking, during the ester exchange process, when there are two types of alkyl groups, four types of ester compositions can be produced according to the following four situations: a situation where the alkoxide of the alcohol attacks the carbons of three ester (RCOOR") groups present in the ester compound; a situation where the alkoxide of the alcohol attacks the carbons of two ester (RCOOR") groups present in the ester compound; a situation where the alkoxide of the alcohol attacks the carbons of one ester (RCOOR") group present in the ester compound; and an unreacted situation where no reaction occurs.

[0087] However, in the aconitate contained in the plasticizer composition according to the present invention, when two ester groups are exchanged or one ester group is exchanged according to the bonding position of the ester group, each may form three types, and therefore, a maximum of 8 compounds may exist in the final composition. However, in the isomer mixture of hexanol according to the present invention, there are two types of alkyl groups, and thus the types may be more diverse.

[0088] Furthermore, unlike acid-alcohol esterification, transesterification does not cause wastewater problems.

[0089] The composition ratio of the mixture prepared by the transesterification reaction can be controlled according to the amount of alcohol added. The amount of alcohol added can be 0.1 to 200 parts by weight, particularly 1 to 150 parts by weight, and more particularly 5 to 100 parts by weight relative to 100 parts by weight of the trialkyl aconitate compound. For reference, the component ratio in the final composition can be determined by the amount of alcohol added in the direct esterification.

[0090] According to an embodiment of the present invention, the transesterification can be carried out at a reaction temperature of 120°C to 190°C, preferably 135°C to 180°C, more preferably 141°C to 179°C, for 10 minutes to 10 hours, preferably 30 minutes to 8 hours, more preferably 1 hour to 6 hours. When the temperature and time are within the above range, the composition ratio of the final plasticizer composition can be effectively controlled. In this case, the reaction time can be determined from the point at which the reaction temperature is reached after the reactant temperature is raised.

[0091] The transesterification may be carried out in the presence of an acid catalyst or a metal catalyst, in which case the reaction time can be shortened.

[0092] The acid catalyst may include, for example, sulfuric acid, methanesulfonic acid, or p-toluenesulfonic acid, and the metal catalyst may include, for example, an organic metal catalyst, a metal oxide catalyst, a metal salt catalyst, or a metal itself.

[0093] For example, the metal component may be any one selected from the group consisting of tin, titanium and zirconium, or a mixture of two or more thereof.

[0094] In addition, after the esterification process, it is further possible to include removing unreacted alcohol and reaction byproducts by distillation. For example, the distillation can be, for example, a two-stage distillation, by which the boiling point difference is utilized to separate alcohol and byproducts separately. In another example, the distillation can be a mixed distillation, in which case a relatively stable ester-based plasticizer composition with a desired ratio can be obtained. Mixed distillation means that unreacted alcohol and byproducts are distilled together.

[0095] According to another embodiment of the present invention, a resin composition including a plasticizer composition and a resin is provided.

[0096] As the resin, resins known in the art can be used. For example, one or more mixtures selected from the following group can be used without limitation: linear vinyl chloride polymers, pasty vinyl chloride polymers, ethylene-vinyl acetate copolymers, ethylene polymers, propylene polymers, polyketones, polystyrene, polyurethane, polylactic acid, natural rubber, synthetic rubber, and thermoplastic elastomers.

[0097] The content of the plasticizer composition may be 5 to 150 parts by weight, preferably 5 to 130 parts by weight, or 10 to 120 parts by weight, relative to 100 parts by weight of the resin.

[0098] Generally, a resin product can be prepared from a resin using a plasticizer composition by melt processing or plasto processing, and a resin obtained by melt processing and a resin obtained by plasto processing can be produced in different ways according to each polymerization method.

[0099] For example, when a vinyl chloride polymer is used for melt processing, solid resin particles with a larger average particle size are prepared by suspension polymerization or the like and used, and this type of vinyl chloride polymer is called a linear vinyl chloride polymer. When a vinyl chloride polymer is used for plastic solution processing, a sol-state resin as tiny resin particles is prepared by emulsion polymerization or the like and used, and this type of vinyl chloride polymer is called a paste-like vinyl chloride resin.

[0100] In this case, in the case of a linear vinyl chloride polymer, the content of the plasticizer is preferably 5 to 80 parts by weight relative to 100 parts by weight of the polymer, and in the case of a paste vinyl chloride polymer, the content of the plasticizer is preferably 40 to 120 parts by weight relative to 100 parts by weight of the polymer.

[0101] The resin composition may further include a filler. The filler may be used in an amount of 0 to 300 parts by weight, preferably 50 to 200 parts by weight, and more preferably 100 to 200 parts by weight, relative to 100 parts by weight of the resin.

[0102] As fillers, fillers known in the art can be used, and are not particularly limited. For example, the filler can be a mixture of one or more selected from silicon dioxide, magnesium carbonate, calcium carbonate, hard coal, talc, magnesium hydroxide, titanium dioxide, magnesium oxide, calcium hydroxide, aluminum hydroxide, aluminum silicate, magnesium silicate and barium sulfate.

[0103] In addition, the resin composition may further include other additives such as stabilizers when necessary. The content of each other additive such as stabilizer is, for example, 0 to 20 parts by weight, preferably 1 to 15 parts by weight, relative to 100 parts by weight of the resin.

[0104] For example, the stabilizer may be a calcium zinc type (Ca-Zn type) stabilizer such as calcium zinc complex stearate or a barium zinc type (Ba-Zn type) stabilizer, but is not particularly limited.

[0105] The resin composition can be applied to the above-mentioned melt processing and plasto processing, and a calendering process, an extrusion process, or an injection process can be applied to the melt processing, and a coating process or the like can be applied to the plasto processing.

[0106] Example

[0107] Below, the present invention will be described in detail with reference to embodiment. However, embodiments according to the present invention may be modified into other various forms, and the scope of the present invention should not be construed as being limited only to the embodiments described below. Examples of the present invention are provided to more fully describe the present invention to those skilled in the art.

[0108] Example 1

[0109] In a reactor equipped with a stirrer, a condenser and a decanter, 452.7 g of aconitic acid, 1035.1 g of an isomer mixture of hexanol and 1.5 g of tetrabutyl titanate (TnBT) were added and esterified in nitrogen. After the reaction was terminated, the catalyst and the product obtained therefrom were neutralized with an alkaline aqueous solution, and unreacted alcohol and water were purified to finally obtain a plasticizer composition.

[0110] The alcohol composition of the hexanol isomer mixture used herein is a mixture of 1-hexanol, 2-methylpentanol, 3-methylpentanol, and cyclopentylmethanol in a weight ratio of 10:40:45:5.

[0111] Example 2

[0112] A plasticizer composition was obtained in the same manner as in Example 1, except that a hexanol isomer mixture of 1-hexanol, 2-methylpentanol, and 3-methylpentanol mixed in a weight ratio of 20:35:45 was used.

[0113] Example 3

[0114] A plasticizer composition was obtained in the same manner as in Example 1, except that a hexanol isomer mixture of 1-hexanol, 2-methylpentanol, 3-methylpentanol, and cyclopentylmethanol mixed in a weight ratio of 10:45:30:15 was used.

[0115] Comparative Example 1

[0116] Dioctyl phthalate (DOP, LG Chem) was used as a plasticizer.

[0117] Comparative Example 2

[0118] Diisononyl phthalate (DINP, LG Chemical) was used as a plasticizer.

[0119] Comparative Example 3

[0120] Di(2-ethylhexyl) terephthalate (GL300, LG Chemical) was used as a plasticizer.

[0121] Comparative Example 4

[0122] A plasticizer composition was obtained in the same manner as in Example 1, except that 493 g of citric acid was used instead of aconitic acid.

[0123] Comparative Example 5

[0124] A plasticizer composition was obtained in the same manner as in Comparative Example 5, except that after esterification, acetic anhydride was added and acetylation was performed.

[0125] Comparative Example 6

[0126] A plasticizer composition was obtained in the same manner as in Example 1, except that 1035.1 g of 2-methylpentanol single compound was used instead of the isomer mixture of hexanol.

[0127] Comparative Example 7

[0128] A plasticizer composition was obtained in the same manner as in Example 1, except that 680 g of a single compound of n-pentanol was used instead of the isomer mixture of hexanol.

[0129] Comparative Example 8

[0130] A plasticizer composition was obtained in the same manner as in Example 1, except that 890 g of a single compound of n-heptanol was used instead of the isomer mixture of hexanol.

[0131] The types of acids and alcohols used in Examples and Comparative Examples are shown in Table 1 below.

[0132] [Table 1]

[0133]

[0134] AA: Aconitic acid

[0135] CA: Citric acid

[0136] ACA: Acetyl Citric Acid

[0137] 1-H: 1-Hexanol

[0138] 2-MP:2-Methylpentanol

[0139] 3-MP:3-Methylpentanol

[0140] CYP-M: Cyclopentylcarbinol

[0141] Experimental Example 1: Sheet Performance Evaluation

[0142] Using the plasticizers of Examples and Comparative Examples, test specimens were prepared according to ASTM D638 and the following formulations and preparation conditions.

[0143] (1) Formulation: 100 parts by weight of linear vinyl chloride polymer (LS100S), 40 parts by weight of plasticizer and 3 parts by weight of stabilizer (BZ-153T).

[0144] (2) Stirring: Stir at 700 rpm at 98°C

[0145] (3) Preparation of samples: 1T, 2T and 3T sheets were prepared by rolling at 160° C. for 4 minutes and by pressing at 180° C. for 2.5 minutes (low pressure) and 2 minutes (high pressure).

[0146] (4) Evaluation items

[0147] 1) Hardness: Shore hardness at 25°C (Shore "A" and "D") is measured using a 3T test specimen for 10 seconds using ASTM D2240. When the a value is smaller, the plasticizing efficiency is determined to be excellent.

[0148] 2) Tensile strength and tensile strength retention: According to the method of ASTM D638, the sample was pulled at a crosshead speed of 200 mm / min using a UTM tester (manufacturer: Instron, model name: 4466), and the breaking point of the 1T sample was determined. The tensile strength was determined as follows.

[0149] Tensile strength (kgf / cm 2 ) = load value (kgf) / thickness (cm) × width (cm)

[0150] The tensile strength retention rate refers to the ratio of the tensile strength remaining in the sample after the sample is placed in an oven at 100°C for 168 hours. The determination method is the same as the tensile strength determination method mentioned above.

[0151] 3) Measurement of tensile elongation and tensile elongation retention: According to the method of ASTM D638, a sample was pulled at a crosshead speed of 200 mm / min using a UTM testing machine, and the breaking point of the 1T sample was determined.

[0152] Tensile elongation (%) = elongated length / initial length × 100

[0153] The tensile elongation retention rate refers to the ratio of the tensile elongation remaining in the sample after the sample is placed in an oven at 100° C. for 168 hours. The determination method is the same as the above-mentioned tensile elongation determination method.

[0154] 4) Measurement of migration loss: According to KSM-3156, obtain a sample with a thickness of more than 2 mm, attach glass plates to both sides of the 1T sample, and apply 1 kgf / cm 2 The sample was placed in a hot air convection oven (80°C) for 72 hours, then removed from the oven and cooled at room temperature for 4 hours. After that, the glass plates attached to both sides of the sample were removed, and the weight of the sample together with the glass plates before and after being placed in the oven was measured, and the migration loss was determined by the following equation.

[0155] Migration loss (%) = {(initial weight of the sample at room temperature - weight of the sample after being placed in the oven) / initial weight of the sample at room temperature} × 100

[0156] 5) Measurement of volatilization loss: The sample prepared above was treated at 80°C for 72 hours, and the weight of the sample was measured.

[0157] Volatilization loss (wt%) = initial sample weight - (sample weight after treatment at 80°C for 72 hours) / initial sample weight × 100

[0158] 6) Stress test (stress resistance): Place a 2 mm thick specimen in a bent state at 23°C for 168 hours, observe its migration degree (exudation degree), and report the result in numerical form. When the value is close to 0, it indicates excellent performance.

[0159] 7) Measurement of Absorption Rate: The absorption rate was evaluated by measuring the time required for the torque of the mixer to stabilize when mixing the resin and the plasticizer.

[0160] (5) Evaluation results

[0161] The evaluation results of the project are shown in Tables 2 and 3 below.

[0162] [Table 2]

[0163]

[0164] [Table 3]

[0165]

[0166] With reference to Table 2 and Table 3 above, it can be seen that the Examples 1 to 3 of the plasticizer compositions according to the embodiments of the present invention are applied, showing similar levels in plasticizing efficiency, mobility and volatility loss, and even compared with the Comparative Example 1 known as a common phthalate-based plasticizer, showing better tensile strength and elongation. In addition, Examples 1 to 3 show similar results in mobility and mechanical properties, and show improved plasticizing efficiency and absorptivity compared with the Comparative Example 2 as another phthalate plasticizer. Considering that different from common phthalate plasticizers, aconitate plasticizers of the present invention are environmentally friendly, the above results show that aconitate plasticizers of the present invention can be used by fully replacing common phthalate plasticizer products.

[0167] In addition, Comparative Example 3 is a commercially available terephthalate plasticizer product, which is used to replace the phthalate plasticizers in Comparative Examples 1 and 2. Its migration loss and stress resistance are much lower than those of the embodiments, and it is also inferior in plasticizing efficiency and absorption rate.

[0168] Meanwhile, in Comparative Examples 4 and 5, which used an isomer mixture of hexanol in the same manner as Examples 1 to 3 of the present invention, but used citric acid or acetylcitric acid instead of aconitic acid, Comparative Example 4 using citric acid showed tensile properties and elongation properties inferior to those of the examples, and Comparative Example 5 using citric acid and further acetylation showed plasticizing efficiency, elongation properties, migration, stress resistance and absorption rate inferior to those of the examples. That is, the results show that the improved physical properties of the present invention can be achieved only when aconitic acid is used as a carboxylic acid.

[0169] In addition, in Comparative Example 6 using single 2-methylpentanol instead of the hexanol isomer mixture used in the present invention, it was shown that both the tensile strength and the elongation were inferior to those of the examples. The results show that when the isomer mixture of hexanol is used instead of a single alcohol, improvement in mechanical properties can be achieved.

[0170] Finally, Comparative Example 7 using an alcohol having 5 carbon atoms instead of the isomer mixture of hexanol used in the present invention showed significantly inferior tensile properties, elongation properties, volatile loss and stress resistance to those of the examples. Comparative Example 8 using an alcohol having 7 carbon atoms showed inferior plasticizing efficiency and tensile properties and elongation properties to those of the examples, and showed that migration, stress resistance and absorption rate were all inferior to those of the examples.

[0171] The above results show that, as in the examples of the present invention, when the esterification product of the isomeric mixture of aconitic acid and hexanol is used as a plasticizer, a plasticizer that can fully replace common products and exhibit excellent performance can be obtained. In particular, in the present invention, when the isomeric mixture of aconitic acid and hexanol is selected and used as the acid and the alcohol, a plasticizer composition having an excellent balance between various physical properties and also having excellent overall physical properties can be provided.

Claims

1. An aconitate plasticizer composition, comprising an aconitate composition containing at least one aconitate of the following formula 1, wherein the alkyl group of the aconitate is derived from an isomeric mixture of hexanol, and The isomeric mixture of hexanol 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, in, The degree of branching of the isomer mixture of hexanol is less than 1.5, [Formula 1] Among them, in the above formula 1, R1 to R3 are each independently a n-hexyl group, a branched hexyl group or a cyclopentylmethyl group.

2. The plasticizer composition according to claim 1, wherein The isomeric mixture of hexanol comprises 1-hexanol, 2-methylpentanol and 3-methylpentanol.

3. The plasticizer composition according to claim 1, wherein The isomer mixture of hexanol includes 40 parts by weight or more of branched alcohol relative to 100 parts by weight of the isomer mixture of hexanol.

4. The plasticizer composition according to claim 1, wherein The isomer mixture of hexanol includes 50 to 95 parts by weight of branched alcohol relative to 100 parts by weight of the isomer mixture of hexanol.

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

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

7. The plasticizer composition according to claim 6, wherein The isomer mixture of hexanol includes 20 parts by weight or less of cyclopentylmethanol relative to 100 parts by weight of the isomer mixture of hexanol.

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. The resin composition according to claim 8, wherein The resin is one or more selected from the group consisting of linear vinyl chloride polymers, pasty vinyl chloride polymers, ethylene-vinyl acetate copolymers, ethylene polymers, propylene polymers, polyketones, polystyrenes, polyurethanes, polylactic acid, natural rubbers, and synthetic rubbers.

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