Propane tricarboxylate-based plasticizer composition and resin composition containing the same

Abstract

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

Description

Technical Field

[0001] The present invention relates to a plasticizer composition containing an isomer mixture of hexyl alcohol and a propane tricarboxylate having an alkyl group derived from benzyl alcohol, and a resin composition containing the same.

Background Art

[0002] Generally, a plasticizer is formed by reacting an alcohol with a polycarboxylic acid such as phthalic acid and adipic acid to form a corresponding ester. Also, in consideration of domestic and foreign regulations on phthalate-based plasticizers harmful to the human body, research on plasticizer compositions that can be used in place of phthalate-based plasticizers such as terephthalate-based, adipate-based, and other polymer-based plasticizers has been continuing.

[0003] On the other hand, regardless of the plastisol industry such as floor materials, wallpapers, soft and hard sheets, the calendaring industry, and the extrusion / injection compound industry, the need for such environmentally friendly products is increasing. In order to enhance the quality characteristics, processability, and productivity for each finished product, it is necessary to use an appropriate plasticizer in consideration of discoloration and migration properties, mechanical physical properties, etc.

[0004] According to the tensile strength, elongation rate, light resistance, migration property, gelation property, absorption rate, etc., which are characteristics required for each industry in such various use areas, auxiliary raw materials such as plasticizers, fillers, stabilizers, viscosity reducers, dispersants, defoamers, foaming agents, etc. are blended with the PVC resin.

[0005] As an example, when applying di(2-ethylhexyl) terephthalate (DEHTP), which is relatively inexpensive and most widely used among plasticizer compositions applicable to PVC, the hardness or sol viscosity is high, the absorption rate of the plasticizer is relatively slow, and the migration property and stress migration property are not good.

[0006] As an improvement measure, as a composition containing DEHTP, it is conceivable to apply the product of the transesterification reaction with butanol as a plasticizer. Although the plasticization efficiency is improved, the loss on heating, thermal stability, etc. are inferior, and the mechanical properties are somewhat reduced. Therefore, improvement in physical properties is required. Generally, there is no solution at present other than adopting a method of complementing this by mixing with other secondary plasticizers.

[0007] However, when applying a secondary plasticizer, it is difficult to predict changes in physical properties, and it may act as a factor for increasing the product unit price. Except in specific cases, improvement in physical properties is not clearly shown, and there are drawbacks such as causing problems in compatibility with the resin, and unexpected problems occur.

[0008] Also, when applying substances such as tris(2-ethylhexyl) trimellitate or triisononyl trimellitate as trimellitate-based products to improve the poor migration properties and weight loss characteristics of the DEHTP product, although the migration properties and weight loss characteristics are improved, there is a problem that the plasticization efficiency decreases and a considerable amount must be added to give an appropriate plasticization effect to the resin. Therefore, in terms of being a relatively high-cost product, it is in a situation where commercialization is impossible.

[0009] Therefore, there is a situation where development of products for solving environmental problems of phthalate-based products as existing products or products with improved poor physical properties of environmentally friendly products for improving environmental problems of phthalate-based products is required.

Summary of the Invention

Problems to be Solved by the Invention

[0010] An object of the present invention is to provide a plasticizer composition that contains a propane tricarboxylate in which the alkyl group is derived from an isomer mixture of hexyl alcohol and benzyl alcohol as a plasticizer composition, and can maintain mechanical properties and stress resistance at the same or higher levels compared to existing plasticizers, and can improve migration properties, plasticization efficiency, and loss on heating. [Means for Solving the Problems]

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

[0012] (1) Specifically, the present invention includes a propane tricarboxylate-based composition containing one or more propane tricarboxylates represented by the following Chemical Formula 1, and the alkyl group of the propane tricarboxylate is derived from an alcohol composition containing an isomer mixture of hexyl alcohol and benzyl alcohol, and the isomer mixture of hexyl alcohol is 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 provides a tricarboxylate-based plasticizer composition containing two or more of them.

[0013] [Chemical Formula 1] [Chemical Structure] In the above Chemical Formula 1, R1 to R3 are each independently an n-hexyl group, a branched hexyl group, a cyclopentylmethyl group, or a benzyl group.

[0014] (2) In the above (1), the present invention provides a plasticizer composition in which the propane tricarboxylate-based composition contains one or more selected from the propane tricarboxylates represented by the following Chemical Formulas 2 to 7. [Chemical Formula 2] [Chemical Structure] [Chemical Formula 3] [Chemical Structure] [Chemical Formula 4]

Chem.

Chem.

Chem.

Chem.

[0015] (3) The present invention provides a plasticizer composition in the above (1) or (2), wherein the isomer mixture of the hexyl alcohol has a branching degree of 2.0 or less.

[0016] (4) The present invention provides a plasticizer composition in any one of the above (1) to (3), wherein the isomer mixture of the hexyl alcohol has a branching degree of 1.5 or less.

[0017] (5) The present invention provides a plasticizer composition in any one of the above (1) to (4), wherein the isomer mixture of the hexyl alcohol contains 1-hexanol, 2-methylpentanol and 3-methylpentanol.

[0018] (6) The present invention provides a plasticizer composition in any one of the above (1) to (5), wherein the isomer mixture of the hexyl alcohol contains 40 parts by weight or more of a branched alcohol with respect to 100 parts by weight of the isomer mixture.

[0019] (7) In any one of the above (1) to (6), the present invention provides a plasticizer composition in which the isomer mixture of hexyl alcohol contains 50 to 95 parts by weight of a branched alcohol with respect to 100 parts by weight of the isomer mixture.

[0020] (8) In any one of the above (1) to (7), the present invention provides a plasticizer composition in which the isomer mixture of hexyl alcohol contains 40 parts by weight or less of 1-hexanol with respect to 100 parts by weight of the isomer mixture.

[0021] (9) In any one of the above (1) to (8), the present invention provides a plasticizer composition in which the isomer mixture of hexyl alcohol contains 1-hexanol, 2-methylpentanol, 3-methylpentanol, and cyclopentylmethanol.

[0022] (10) In any one of the above (1) to (9), the present invention provides a plasticizer composition in which the isomer mixture of hexyl alcohol contains 20 parts by weight or less of cyclopentylmethanol with respect to 100 parts by weight of the isomer mixture.

[0023] (11) In any one of the above (1) to (10), the present invention provides a plasticizer composition in which the weight ratio of the isomer mixture of hexyl alcohol to benzyl alcohol is 90:10 to 10:90.

[0024] (12) The present invention provides a resin composition containing 100 parts by weight of a resin and 5 to 150 parts by weight of the plasticizer composition according to any one of the above (1) to (11).

[0025] (13) In the above (12), the present invention provides a resin composition in which the resin is at least one selected from the group consisting of a straight 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.

Advantages of the Invention

[0026] When the plasticizer composition according to an embodiment of the present invention is used in a resin composition, compared with existing plasticizers, it can maintain and improve mechanical properties and stress resistance at an equivalent or higher level, and can improve physical properties such as weight reduction characteristics, migration properties, and plasticization efficiency.

Mode for Carrying Out the Invention

[0027] The terms and words used in this specification and the claims should not be construed as being limited to their ordinary or dictionary meanings. In accordance with the principle that the inventors can appropriately define the concepts of the terms in order to explain their invention in the best way, they should be construed in meanings and concepts consistent with the technical idea of the present invention.

[0028] Definition of Terms The term "composition" as used in this specification includes not only reaction products and decomposition products formed from the materials of the composition, but also mixtures of materials including the composition.

[0029] The term "straight vinyl chloride polymer" as used in this specification is one type of vinyl chloride polymer, and can mean a polymer polymerized by suspension polymerization, bulk polymerization, etc., and has a form of porous particles with a large number of pores distributed in the size range of several tens to several hundreds of micrometers, and means a polymer that has no cohesiveness and excellent fluidity.

[0030] The term "paste vinyl chloride polymer" as used in this specification is one type of vinyl chloride polymer, and can mean a polymer polymerized by fine suspension polymerization, fine seed polymerization, or emulsion polymerization, etc., and means a polymer that has cohesiveness and poor fluidity as fine and dense particles having a size range of several tens to several thousands of nanometers.

[0031] The terms "comprising," "having," and derivatives thereof are not intended to exclude the presence of any additional components, steps, or procedures, whether or not specifically disclosed. To avoid any uncertainty, all compositions claimed by use of the term "comprising" can, unless conversely described, include any additional additives, adjuvants, or compounds, whether polymeric or otherwise. In contrast, the term "consisting essentially of" excludes from the scope of any successive description any other components, steps, or procedures that are not operationally essential. The term "consisting of" excludes any component, step, or procedure not specifically described or recited.

[0032] Measurement Method In this specification, the analysis of the content of components in a composition is performed by gas chromatography measurement, and analyzed by a gas chromatography instrument manufactured by Agilent (product name: Agilent 7890 GC, column: HP-5, carrier gas: helium (flow rate 2.4 mL / min), detector: F.I.D, injection volume: 1 μL, initial value: 70 °C / 4.2 min, final value: 280 °C / 7.8 min, program rate: 15 °C / min).

[0033] In this specification, "hardness" means the Shore hardness (Shore "A" and / or Shore "D") at 25 °C according to ASTM D2240, measured under the conditions of 3T 10s, and can be an index for evaluating the plasticization efficiency, meaning that the lower it is, the better the plasticization efficiency.

[0034] In this specification, the "tensile strength" is measured according to the ASTM D638 method using a U.T.M (manufacturer: Instron, model: 4466) as the test equipment. After pulling at a cross head speed of 200 mm / min (1T), the point where the test piece is cut is measured and calculated using the following mathematical formula 1.

[0035] [Mathematical formula 1] Tensile strength (kgf / cm2) = Load value (kgf) / Thickness (cm) × Width (cm)

[0036] In this specification, the "elongation rate" is measured according to the ASTM D638 method using the above U.T.M. After pulling at a cross head speed of 200 mm / min (1T), the point where the test piece is cut is measured and calculated using the following mathematical formula 2.

[0037] [Mathematical formula 2] Elongation rate (%) = Length after elongation / Initial length × 100

[0038] In this specification, the "migration loss" is carried out according to KSM-3156. After obtaining a test piece with a thickness of 2 mm or more and attaching glass plates to both sides of the test piece, a load of 1 kgf / cm2 is applied. After leaving the test piece in a hot air circulation oven (80 °C) for 72 hours, it is taken out and cooled at room temperature for 4 hours. Then, after removing the glass plates attached to both sides of the test piece, the weights of the glass plates and the specimen plate before and after leaving them in the oven are measured, and the migration loss amount is calculated by the following mathematical formula 3.

[0039] [Mathematical formula 3] Migration loss amount (%) = { (Weight of the initial test piece) - (Weight of the test piece after being left in the oven) / (Weight of the initial test piece)} × 100

[0040] In this specification, "volatile loss" means that after the test piece is operated at 80 °C for 72 hours, the weight of the test piece is measured.

[0041] [Formula 4] Volatile loss (%) = { (weight of the initial test piece) - (weight of the test piece after operation) / (weight of the initial test piece)} × 100

[0042] 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. When they are different, the measurement methods and conditions shall be clearly specified separately.

[0043] Hereinafter, in order to facilitate the understanding of the present invention, the present invention will be described in more detail.

[0044] According to an embodiment of the present invention, a propane tricarboxylate-based composition containing 1 or more of the propane tricarboxylates of the following Chemical Formula 1 is provided. The alkyl group of the propane tricarboxylate is derived from an alcohol composition containing an isomer mixture of hexyl alcohol and benzyl alcohol. The isomer mixture of hexyl alcohol contains 2 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. A tricarboxylate-based plasticizer composition is provided.

[0045] [Chemical Formula 1] [Chemical Structure]

[0046] In the above Chemical Formula 1, R1 to R3 are each independently an n-hexyl group, a branched hexyl group, a cyclopentylmethyl group or a benzyl group.

[0047] The plasticizer composition can be a product produced by a direct esterification reaction of 1,2,3-propanetricarboxylic acid or its derivative with a hexyl alcohol mixture and an alcohol composition containing benzyl alcohol, or a transesterification reaction of a trialkyl 1,2,3-tricarboxylate with the alcohol composition. At this time, the mixture of hexyl alcohols applied can be a mixture of hexyl alcohols having different structures from each other, that is, a mixture of structural isomers. More specifically, the isomer mixture of the hexyl alcohol can contain 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.

[0048] In the above esterification reaction or transesterification reaction, depending on the composition ratio of the hexyl alcohol mixture and benzyl alcohol in the alcohol composition used as a reactant, or the alcohol contained in the hexyl alcohol isomer mixture, the alkyl groups of R1 to R3 in Chemical Formula 1 can be determined. The final composition can include various compositions in which 3, 2 or 1 isomer alkyl group of hexyl alcohol and benzyl group are respectively bonded to the three alkyl groups. The ratio of the components in the final composition can be determined according to the ratio of each structural isomer component in the reacting hexyl alcohol mixture and the ratio of the hexyl alcohol isomer mixture and benzyl alcohol in the alcohol composition.

[0049] Thus, when applying a tricarboxylate plasticizer and using an alkyl group derived from an alcohol composition containing an isomer mixture of hexyl alcohol and benzyl alcohol, improved migration properties, heat loss, and tensile strength can be exhibited compared to those derived from an isomer mixture of hexyl alcohol alone, and better mechanical properties can be provided compared to those derived from an alcohol having less than 6 carbon atoms in the alkyl group. More specifically, the tensile strength, elongation rate, and heat loss can be significantly improved, the plasticization efficiency can be excellent compared to the case where the number of carbon atoms in the alkyl group exceeds 6, and the migration resistance and stress resistance can be more excellent.

[0050] More specifically, the propane tricarboxylate composition can contain one or more selected from propane tricarboxylates of the following Chemical Formulas 2 to 7, and particularly preferably, can contain all of the propane tricarboxylates of the following Chemical Formulas 2 to 7.

[0051] [Chemical Formula 2] [Chem.]

[0052] [Chemical Formula 3] [Chem.]

[0053] [Chemical Formula 4] [Chem.]

[0054] [Chemical Formula 5] [Chem.]

[0055] [Chemical Formula 6] [Chem.]

[0056] [Chemical Formula 7] [Chem.]

[0057] In the above Chemical Formulas 2 to 7, R a is each an n-hexyl group, a branched hexyl group or a cyclopentylmethyl group, R b is a benzyl group.

[0058] The tricarboxylates represented by the above Chemical Formulas 2 to 7 mean those in which all alkyl groups are derived from a hexyl alcohol isomer mixture (Chemical Formula 2), those in which two alkyl groups are derived from a hexyl alcohol isomer mixture and one alkyl group is derived from benzyl alcohol (Chemical Formulas 3 and 4), those in which one alkyl group is derived from a hexyl alcohol isomer mixture and two alkyl groups are derived from benzyl alcohol (Chemical Formulas 5 and 6), and those in which all alkyl groups are derived from benzyl alcohol (Chemical Formula 7). The relative ratios of the respective tricarboxylates represented by the above Chemical Formulas 2 to 7 in the plasticizer composition of the present invention may vary depending on the composition ratio of the hexyl alcohol isomer mixture and benzyl alcohol in the alcohol composition used in the esterification reaction or transesterification reaction.

[0059] On the one hand, the degree of branching of the hexyl alcohol isomer mixture contained in the alcohol composition of the present invention can be 2.0 or less, preferably 1.5 or less, particularly preferably 1.0 or less. Specifically, the degree of branching can be 1.5 or less, can be 1.3 or less, and more preferably can be 1.1 or less. Also, it can be 0.1 or more, can be 0.2 or more, can be 0.3 or more, and most preferably can be 0.7 or more. The degree of branching of this isomer mixture of hexyl alcohol can be similarly maintained in the tricarboxylate-based plasticizer composition produced from hexyl alcohol. If the degree of branching is too high, the balance between physical properties may be disrupted, and problems may occur where the product fails to meet one or more of the evaluation criteria. However, when it is 1.5 or less as a preferred range, not only mechanical physical properties but also improvements in migration loss and heat loss can be more optimized, and the balance between physical properties can be excellent.

[0060] Here, the degree of branching can mean how many branched carbons the alkyl group bonded to the substance contained in the composition has, and the degree can 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 methylpentanol, and 10% by weight of ethylbutanol, the number of branched carbons of each alcohol is 0, 1, and 2 respectively, and the degree of branching can be calculated as [(60×0)+(30×1)+(10×2)] / 100 and is 0.5. On the other hand, when defining the degree of branching of the present invention, in the case of cyclopentylmethanol, the number of branched carbons is regarded as 0.

[0061] The hexyl alcohol isomer mixture can contain 1-hexanol and 2-methylpentanol. Thus, when both 1-hexanol and 2-methylpentanol are contained in the isomer mixture, the balance between physical properties can be maintained, and an excellent effect in terms of heat loss can be obtained. Preferably, it can further contain 3-methylpentanol, and in this case, there is an advantage that the balance between physical properties is very excellent.

[0062] The branched hexyl alcohol containing the 2-methylpentanol can be contained in an amount of 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, based on 100 parts by weight of the isomer mixture. As the maximum amount, it can be all branched, and can be contained in an amount of 99 parts by weight or less, 98 parts by weight, preferably 95 parts by weight or less, or 90 parts by weight or less. Within this range, when the branched hexyl alcohol is contained, improvement in mechanical properties can be expected.

[0063] Also, the linear alcohol of the 1-hexanol can be contained in an amount of 50 parts by weight or less, 40 parts by weight or less, 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 can be contained in an amount of at least 2 parts by weight or more. In this case, it can have the advantage of maintaining the balance between physical properties and improving mechanical properties. Although linear alcohols are known to exhibit excellent effects in theory, in the present invention, results different from such theoretical results are obtained, and it is confirmed that when an isomer mixture containing branched alcohols is applied, the balance of physical properties is more excellent.

[0064] Also, the isomer mixture of the hexyl alcohol can contain 1-hexanol, 2-methylpentanol, 3-methylpentanol, and cyclopentylmethanol. Preferably, by further containing cyclopentylmethanol, the balance between physical properties can be maintained, and mechanical properties and plasticization efficiency can be slightly improved.

[0065] In this case, the cyclopentylmethanol can be 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 not be present, or the minimum amount for obtaining the effect thereof can be 2 parts by weight.

[0066] Specifically, by characteristics such as the ratio of branched alkyl groups in the final composition to the total alkyl groups, and further, the ratio of specific branched alkyl groups among the branched alkyl groups, it is possible to balance the plasticizing efficiency and the physical properties of migration / weight loss characteristics, and mechanical physical properties such as tensile strength and elongation at break and stress resistance can also be maintained at an equivalent or higher level, which can be achieved from the components and their component ratios of the isomers of hexyl alcohol described above.

[0067] Thereby, it is possible to eliminate the environmental problems of existing phthalate-based products and realize a product with further improved weight loss characteristics, and it is possible to provide a plasticizer composition with significantly improved migration and weight loss characteristics compared to existing terephthalate-based products.

[0068] On the other hand, in the alcohol composition of the present invention, the weight ratio of the isomer mixture of the hexyl alcohol to benzyl alcohol can be 90:10 to 10:90, preferably 90:10 to 30:70, and particularly preferably 90:10 to 50:50. Within the above range, the plasticizer composition can be excellent in plasticizing efficiency and excellent in migration resistance and stress resistance.

[0069] The method for producing the plasticizer composition according to an embodiment of the present invention is a method well-known in the art and is applicable without particular limitation as long as the above-described plasticizer composition can be produced.

[0070] For example, the composition can be produced by directly subjecting an alcohol composition containing 1,2,3-propanetricarboxylic acid, its anhydride or derivative, an isomer mixture of hexyl alcohol, and benzyl alcohol to an esterification reaction, or the composition can also be produced by subjecting an alcohol composition containing trialkyl 1,2,3-propanetricarboxylate, an isomer mixture of hexyl alcohol, and benzyl alcohol to a transesterification reaction.

[0071] The plasticizer composition according to an embodiment of the present invention is a substance produced by appropriately performing the esterification reaction. As long as it meets the above conditions and the weight ratio between tricarboxylates of each system is preferably adjusted, the production method is not particularly limited.

[0072] As an example, the direct esterification reaction includes steps of adding an alcohol composition containing 1,2,3 - propanetricarboxylic acid or its derivative, an isomer mixture of hexyl alcohol, and benzyl alcohol, then adding a catalyst and reacting under a nitrogen atmosphere; removing unreacted raw materials; neutralizing (or deactivating) unreacted raw materials and the catalyst; and removing (e.g., by vacuum distillation) and filtering impurities.

[0073] The components and weight ratio of the isomer mixture of hexyl alcohol are as described above. The alcohol composition containing the isomer mixture of hexyl alcohol and benzyl alcohol can be used in the range of 200 - 900 mol%, 200 - 700 mol%, 200 - 600 mol%, 250 - 600 mol%, or 270 - 600 mol% based on 100 mol% of the acid. By controlling the content of this alcohol, the component ratio in the final composition can be controlled.

[0074] The catalyst can be one or more selected from, for example, 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 sulfuric 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 organometals such as tetraalkyl titanate and its polymers. As a specific example, tetraalkyl titanate can be used as the catalyst. Preferably, as acid catalysts with a low activation temperature, p - toluenesulfonic acid, methanesulfonic acid, etc. are appropriate.

[0075] The amount of the catalyst used can vary depending on the type. For example, in the case of a homogeneous catalyst, it can be in the range of 0.01 to 5% by weight, 0.01 to 3% by weight, 1 to 5% by weight, or 2 to 4% by weight based on the total 100% by weight of the reactants. Also, in the case of a heterogeneous catalyst, it can be in the range of 5 to 200% by weight, 5 to 100% by weight, 20 to 200% by weight, or 20 to 150% by weight of the total amount of the reactants.

[0076] At this time, the reaction temperature can be in the range of 100 to 280 °C, 100 to 250 °C, or 120 to 230 °C.

[0077] As another example, the transesterification reaction can be the reaction of a trialkyl 1,2,3-propanetricarboxylate with an alcohol composition containing an isomer mixture of the hexyl alcohol and benzyl alcohol. From the perspective of minimizing impurities, the alkyl group of the trialkyl 1,2,3-propanetricarboxylate is preferably a hexyl group or a benzyl group. 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-propanetricarboxylate contains both linear and branched hexyl groups.

[0078] The "transesterification reaction" used in the present invention means a reaction in which an alcohol and an ester react, and as shown in the following Reaction Formula 1, R'' of the ester is mutually exchanged with R' of the alcohol.

[0079] [Reaction Formula 1] [Chemical Formula]

[0080] Generally, when the transesterification reaction is carried out, in the case where there are two types of alkyl groups, when the alkoxide of alcohol attacks the carbon of the three ester (RCOOR'') groups present in the ester compound; when attacking the carbon of the two ester (RCOOR'') groups present in the ester compound; when attacking the carbon of one ester (RCOOR'') group present in the ester compound; in the case of unreacted when the reaction has not been carried out; like this, four types of ester compositions can be produced according to the four cases.

[0081] However, in the case of the tricarboxylate contained in the plasticizer composition according to the present invention, for the case where two ester groups are exchanged and the case where one ester group is exchanged according to the bonding position of the ester group, three types can be formed respectively, whereby up to eight compounds can be mixed in the final composition. However, in the case of the isomer mixture of hexyl alcohol according to the present invention, since there are two or more types of alkyl groups present, the types can be more diverse.

[0082] In addition, the transesterification reaction has the advantage that it does not cause the problem of waste water compared to the esterification reaction between an acid and an alcohol.

[0083] The composition ratio of the mixture produced by the transesterification reaction can be controlled according to the addition amount of the alcohol. The addition amount of the alcohol 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 with respect to 100 parts by weight of the trialkyl 1,2,3 - propanetricarboxylate compound. For reference, what determines the component ratio in the final composition can be the addition amount of the alcohol, as in the direct esterification reaction.

[0084] According to one embodiment of the present invention, the transesterification reaction is preferably carried out at a reaction temperature of 120 to 190 ° C, preferably 135 to 180 ° C, more preferably 141 to 179 ° C for 10 minutes to 10 hours, preferably 30 minutes to 8 hours, 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. At this time, the reaction time can be calculated from the time when the reaction temperature is reached after the reactants are heated.

[0085] The transesterification reaction can be carried out under an acid catalyst or a metal catalyst, in which case the reaction time can be shortened.

[0086] The acid catalyst can be, for example, sulfuric acid, methanesulfonic acid or p-toluenesulfonic acid, and the metal catalyst can be, for example, an organometallic catalyst, a metal oxide catalyst, a metal salt catalyst or the metal itself.

[0087] The metal component can be, for example, any one selected from the group consisting of tin, titanium and zirconium or a mixture of two or more thereof.

[0088] Further, after the transesterification reaction, a step of distilling and removing unreacted alcohol and reaction by-products can be further included. The distillation can be, for example, a two-step distillation that separates separately using the difference in boiling points of the alcohol and the reaction by-products. As still another example, the distillation can be a mixed distillation. In this case, there is an effect that an ester-based plasticizer composition can be relatively stably ensured at a desired composition ratio. The mixed distillation means distilling unreacted alcohol and reaction by-products simultaneously.

[0089] According to another embodiment of the present invention, a resin composition containing the above plasticizer composition and resin is provided.

[0090] As the resin, resins well-known in the art can be used. For example, one or more mixtures selected from the group consisting of straight vinyl chloride polymers, paste vinyl chloride polymers, ethylene vinyl acetate copolymers, ethylene polymers, propylene polymers, polyketones, polystyrenes, polyurethanes, polylactic acids, natural rubbers, synthetic rubbers, and thermoplastic elastomers can be used, but it is not limited thereto.

[0091] 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.

[0092] Generally, the resin in which the plasticizer composition is used can be manufactured as a resin product by melt processing or plastisol processing, and the melt-processed resin and the plastisol-processed resin can be produced to be different according to each polymerization method.

[0093] For example, when a vinyl chloride polymer is used for melt processing, solid resin particles produced by suspension polymerization or the like and having a large average particle size are used. Such a vinyl chloride polymer is referred to as a straight vinyl chloride polymer. When it is used for plastisol processing, a resin in a sol state as fine resin particles produced by emulsion polymerization or the like is used. Such a vinyl chloride polymer is referred to as a paste vinyl chloride resin.

[0094] At this time, in the case of the straight vinyl chloride polymer, the plasticizer is preferably contained in the range of 5 to 80 parts by weight based on 100 parts by weight of the polymer. In the case of the paste vinyl chloride polymer, it is preferably contained in the range of 40 to 120 parts by weight based on 100 parts by weight of the polymer.

[0095] The resin composition can further contain a filler. The filler can be 0 to 300 parts by weight, preferably 50 to 200 parts by weight, more preferably 100 to 200 parts by weight, based on 100 parts by weight of the resin.

[0096] The filler can be a filler well-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.

[0097] In addition, the resin composition can further contain other additives such as stabilizers as needed. The other additives such as the stabilizer can be, for example, 0 to 20 parts by weight, preferably 1 to 15 parts by weight, respectively, based on 100 parts by weight of the resin.

[0098] As the stabilizer, for example, a calcium-zinc (Ca-Zn) stabilizer such as a calcium-zinc composite stearate or a barium-zinc (Ba-Zn) stabilizer can be used, but it is not particularly limited thereto.

[0099] As described above, the resin composition is applicable to both melt processing and plastisol processing. For example, melt processing can apply calendering, extrusion, or injection molding, and plastisol processing can apply coating, etc.

[0100] Example Hereinafter, in order to specifically describe the present invention, examples will be given and described in detail. However, the examples according to the present invention can be deformed into various other forms, and the scope of the present invention should not be construed as being limited to the examples described in detail below. The examples of the present invention are provided to more fully explain the present invention to those with average knowledge in the industry.

[0101] Example 1 Into a reactor equipped with a stirrer, a condenser, and a decanter, 500.2 g of 1,2,3-propanetricarboxylic acid, 867.5 g of an isomer mixture of hexyl alcohol, 371.8 g of benzyl alcohol, and 1.5 g of tetrabutyl titanate (TnBT) were charged. Then, an esterification reaction was carried out under a nitrogen atmosphere to complete the reaction. The catalyst and the product were neutralized with an aqueous alkali solution, and unreacted alcohol and moisture were purified to finally obtain a plasticizer composition.

[0102] The alcohol composition of the isomer mixture of hexyl alcohol used here is a mixture of 1-hexanol, 2-methylpentanol, 3-methylpentanol, and cyclopentylmethanol in a weight ratio of 10:40:45:5.

[0103] Example 2 The same procedure as in Example 1 was carried out, but as the isomer mixture of hexyl alcohol, a mixture of 1-hexanol, 2-methylpentanol, and 3-methylpentanol mixed in a weight ratio of 20:35:45 was used to obtain a plasticizer composition.

[0104] Example 3 The same procedure as in Example 1 was carried out, but as the isomer mixture of hexyl alcohol, a mixture of 1-hexanol, 2-methylpentanol, 3-methylpentanol, and cyclopentylmethanol mixed in a weight ratio of 10:45:30:15 was used to obtain a plasticizer composition.

[0105] Example 4 In Example 1, the total weight of the isomer mixture of hexyl alcohol and benzyl alcohol was used in the same manner, but a plasticizer composition was obtained such that the weight ratio between the two alcohols was 90:10.

[0106] Example 5 In Example 1, the total weight of the isomer mixture of hexyl alcohol and benzyl alcohol was used in the same manner, but a plasticizer composition was obtained such that the weight ratio between the two alcohols was 50:50.

[0107] Comparative Example 1 Dioctyl phthalate (DOP, manufactured by LG Chem) was used as a plasticizer.

[0108] Comparative Example 2 Diisononyl phthalate (DINP, manufactured by LG Chem) was used as a plasticizer.

[0109] Comparative Example 3 Di(2-ethylhexyl) terephthalate (GL300, manufactured by LG Chem) was used as a plasticizer.

[0110] Comparative Example 4 A composition (GL500, manufactured by LG Chem) 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 was used as a plasticizer.

[0111] Comparative Example 5 A plasticizer composition was obtained in the same manner except that 326.4 g of citric acid was used instead of 1,2,3-propanetricarboxylic acid in Example 1.

[0112] Comparative Example 6 A plasticizer composition was obtained in the same manner except that acetic anhydride was added and acetylated after the esterification reaction in Comparative Example 5.

[0113] Comparative Example 7 A plasticizer composition was obtained in the same manner except that only 1239.3 g of an isomer mixture of hexyl alcohol was used without using benzyl alcohol in Example 1.

[0114] Comparative Example 8 A plasticizer composition was obtained in the same manner except that only 1239.3 g of benzyl alcohol was used without using the isomer mixture of hexyl alcohol in Example 1.

[0115] Comparative Example 9 A plasticizer composition was obtained in the same manner except that 867.5 g of 2-methylpentanol single compound was used instead of the isomer mixture of hexyl alcohol in Example 1 above.

[0116] Comparative Example 10 A plasticizer composition was obtained in the same manner except that 820 g of n-butanol single compound was used instead of the isomer mixture of hexyl alcohol in Example 1 above.

[0117] Comparative Example 11 A plasticizer composition was obtained in the same manner except that 1440 g of 2-ethylhexanol single compound was used instead of the isomer mixture of hexyl alcohol in Example 1 above.

[0118] The types of acids and alcohols used in the above Examples and Comparative Examples were summarized and shown in Table 1 below.

[0119]

Table 1

[0120] Experimental Example 1: Evaluation of Sheet Performance Test specimens were prepared according to ASTM D638 under the following formulation and preparation conditions using the plasticizers of the Examples and Comparative Examples.

[0121] (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)

[0122] (2) Mixing: Mixing at 98 °C at 700 rpm

[0123] (3) Preparation of test specimens: Using a roll mill, work at 160 °C for 4 minutes, and using a press, work at 180 °C for 2.5 minutes (low pressure) and 2 minutes (high pressure) to prepare 1T, 2T, and 3T sheets.

[0124] (4) Evaluation items 1) Hardness : In accordance with ASTM D2240, the Shore hardness at 25 °C (Shore "A" and "D") was measured for 10 seconds using a 3T test specimen. The smaller the value, the better the plasticization efficiency is evaluated.

[0125] 2) Tensile Strength and Tensile Strength Retention : In accordance with the method of ASTM D638, using a U.T.M (manufacturer: Instron, model: 4466) as the test equipment, after pulling at a cross head speed of 200 mm / min, the point where the 1T test specimen was cut was measured. The tensile strength was calculated as follows.

[0126] Tensile strength (kgf / cm 2 ) = Load value (kgf) / Thickness (cm) × Width (cm)

[0127] The tensile retention rate measures the ratio of the tensile strength remaining in the test specimen after leaving the test specimen in an oven at 100 °C for 168 hours, and the measurement method is the same as the measurement method of the above-mentioned tensile strength.

[0128] 3) Measurement of Tensile Elongation and Tensile Elongation Retention : In accordance with the method of ASTM D638, after using the U.T.M to pull at a cross head speed of 200 mm / min and measuring the point where the 1T test specimen was cut, the elongation rate was calculated as follows.

[0129] Elongation rate (%) = Length after elongation / Initial length × 100 was calculated.

[0130] The elongation residual rate measures 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 is the same as the measurement method for the elongation rate described above.

[0131] 4) Measurement of Migration Loss : According to KSM-3156, a test piece with a thickness of 2 mm or more was obtained, and after attaching glass plates to both sides of the 1T test piece, a load of 1 kgf / cm2 was applied. After leaving the test piece in a hot air circulation oven (80°C) for 72 hours, it was taken out and cooled at room temperature for 4 hours. Then, after removing the glass plates attached to both sides of the test piece, the weights of the glass plates and the specimen plate before and after being left in the oven were measured, and the migration loss amount was calculated by the following formula. Migration loss amount (%) = {(Initial weight of the test piece at room temperature - Weight of the test piece after being left in the oven) / (Initial weight of the test piece at room temperature)} × 100

[0132] 5) Measurement of Volatile Loss : After working the prepared test piece at 80°C for 72 hours, the weight of the test piece was measured.

[0133] The loss on heating (weight %) was calculated by: (Initial weight of the test piece - Weight of the test piece after working at 80°C for 72 hours) / Initial weight of the test piece × 100.

[0134] 6) Stress Test (Stress Resistance) : After leaving a test piece with a thickness of 2 mm in a bent state at 23°C for 168 hours, the degree of migration (the degree of oozing out) was observed, and the result was described numerically. The closer to 0, the better the characteristics were shown.

[0135] (5) Evaluation results The evaluation results of the above items are shown in Table 2 and Table 3 below.

[0136]

Table 2

[0137]

Table 3

[0138] Referring to Tables 2 and 3 above, in the case of Examples 1 to 5 to which the plasticizer composition according to an embodiment of the present invention was applied, significantly better plasticizing efficiency and migration properties were shown as compared with Comparative Examples 1 and 2 used as existing products, and it was also confirmed that excellent effects were shown in tensile properties and elongation properties. Although Comparative Examples 1 and 2 show excellent performance, they are existing products that are phthalate-based and have problems of not being environmentally friendly. The above results suggest that the plasticizer composition of the present invention that does not contain phthalate and is environmentally friendly can not only fully replace the existing products, but also achieve more improved performance.

[0139] In addition, Comparative Examples 3 and 4 are environmentally friendly products and are products used in place of Comparative Examples 1 and 2. However, there are problems that their migration properties and stress resistance are significantly inferior to those of the existing products and Examples 1 to 5 of the present invention, and they are also inferior to Examples 1 to 5 of the present invention in terms of plasticizing efficiency.

[0140] In addition, Comparative Examples 5 and 6 are similar to Examples 1 to 5 of the present invention in that an isomer mixture of hexyl alcohol is applied. At this time, citric acid or acetylcitric acid is applied instead of 1,2,3-propanetricarboxylic acid. However, in the case of Comparative Example 5 using citric acid, generally inferior effects are shown in plasticizing efficiency, tensile properties, elongation properties, migration properties and stress resistance as compared with Examples 1 to 5. In the case of Comparative Example 6 using acetylcitric acid, it is inferior to Examples 1 to 5 in terms of plasticizing efficiency and elongation rate, and is also somewhat inferior to Examples 1 to 5 in terms of migration loss and stress resistance.

[0141] On the one hand, in Comparative Examples 7 and 8, as the alcohol composition, only one of the isomer mixture of hexyl alcohol and benzyl alcohol was used. However, in the case of Comparative Example 7 using only the isomer mixture of hexyl alcohol, it was inferior to Examples 1 to 5 in terms of tensile strength, migration property, and heat loss. In the case of Comparative Example 8 using only benzyl alcohol, it was inferior to Examples 1 to 5 in terms of plasticization efficiency, elongation property, migration property, and stress resistance. From this, it can be confirmed that by applying both the isomer mixture of benzyl alcohol and hexyl alcohol, the overall physical properties are improved by the synergistic effect of the two alcohols, and the balance between the physical properties is also excellently maintained.

[0142] Finally, in Comparative Example 9, instead of the isomer mixture of hexyl alcohol, 2-methylpentanol, which is one of the hexyl alcohols, was applied alone, showing inferior tensile properties, elongation properties, migration properties, and heat loss compared to Examples 1 to 5. In Comparative Examples 10 and 11, as the alcohol used together with benzyl alcohol, an alcohol with 4 carbon atoms was applied (Comparative Example 10) or an alcohol with 8 carbon atoms was applied (Comparative Example 11). Comparative Example 10 showed a significantly inferior effect in terms of tensile properties and heat loss, and Comparative Example 11 showed a significantly inferior effect in terms of plasticization efficiency, elongation properties, migration properties, and stress resistance. From this, excellent physical properties as in Examples 1 to 5 of the present invention are realized only when an alcohol composition containing an isomer mixture of hexyl alcohol and benzyl alcohol is applied as the alcohol reacting with 1,2,3-propanetricarboxylic acid. When other alcohols are used instead of either of the two alcohols, a phenomenon of deterioration of specific physical properties occurs, and it can be confirmed that a plasticizer composition with excellent performance cannot be provided thereby.

[0143] Thus, when applying the esterification reactant of an alcohol composition containing an isomer mixture of 1,2,3-propanetricarboxylic acid, hexyl alcohol, and benzyl alcohol as a plasticizer as in the examples of the present invention, it was confirmed that an existing product can be sufficiently replaced and a plasticizer exhibiting excellent performance can be realized.

Claims

1. A propanetricarboxylate-based composition containing propanetricarboxylates represented by the following Chemical Formulas 2 to 7, wherein the alkyl group of the propanetricarboxylate is derived from an alcohol composition containing an isomer mixture of hexyl alcohol and benzyl alcohol, the isomer mixture of hexyl alcohol contains 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, and cyclopentylmethanol, and the isomer mixture of hexyl alcohol has a degree of branching of 1.5 or less, a tricarboxylate-based plasticizer composition. 【Chemical 1】 【Chemical Formula 2】 [Chemical 3] [Chemical Formula 4] 【Chemical Formula 5】 【Chemical Formula 6】 In the Chemical Formulas 2 to 7, R ａ is an n-hexyl group, a branched hexyl group or a cyclopentylmethyl group, respectively, R ｂ is a benzyl group.

2. The plasticizer composition according to Claim 1, wherein the isomer mixture of hexyl alcohol contains 1-hexanol, 2-methylpentanol, and 3-methylpentanol.

3. The plasticizer composition according to Claim 1, wherein the isomer mixture of hexyl alcohol contains 40 parts by weight or more of branched alcohol with respect to 100 parts by weight of the isomer mixture.

4. The plasticizer composition according to Claim 1, wherein the isomer mixture of hexyl alcohol contains 50 to 95 parts by weight of branched alcohol with respect to 100 parts by weight of the isomer mixture.

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

6. The plasticizer composition according to Claim 1, wherein the isomer mixture of hexyl alcohol contains 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 with respect to 100 parts by weight of the isomer mixture.

8. The plasticizer composition according to Claim 1, wherein the weight ratio of the isomer mixture of hexyl alcohol to benzyl alcohol is 90:10 to 10:

90.

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

10. The resin composition according to claim 9, wherein the resin is at least one selected from the group consisting of a straight 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.

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