Aconitate plasticizer composition and resin composition containing the same

Abstract

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

Description

Technical Field

[0001] The present invention relates to a plasticizer composition containing aconitate having alkyl groups with various structures within the same number of carbon atoms, 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 the regulations on phthalate-based plasticizers harmful to the human body both in and outside Korea, 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 compounding industry, the need for such environmentally friendly products is increasing. In order to enhance the quality characteristics, processability, and productivity of finished products for this, it is necessary to use an appropriate plasticizer considering 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 by each industry in such various usage 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 commonly used among the 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 either.

[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 weight loss on heating and thermal stability are inferior, and the mechanical properties are somewhat reduced. Therefore, improvement of physical properties is required. Generally, there is no solution at present except to adopt 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 of physical properties is not clearly shown, and problems that cannot be predicted, such as causing problems in compatibility with the resin, occur.

[0008] In addition, in order to improve the poor migration properties and weight loss characteristics of the DEHTP product, when applying substances such as tris(2-ethylhexyl) trimellitate and triisononyl trimellitate as trimellitate-based products, 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 product with a relatively high unit price, 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 aconitate in which the alkyl group is derived from an isomer mixture of hexyl 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 plasticization efficiency and migration resistance.

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] Specifically, (1) the present invention includes an aconitate-based composition containing one or more aconitates of the following Chemical Formula 1, wherein the alkyl group of the aconitate is derived from an isomer mixture of hexyl 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 an aconitate-based plasticizer composition containing two or more thereof. [Chemical Formula 1]

Chemical

[0013] (2) In the above (1), the present invention provides a plasticizer composition in which the isomer mixture of hexyl alcohol has a degree of branching of 2.0 or less.

[0014] (3) In the above (1) or (2), the present invention provides a plasticizer composition in which the isomer mixture of hexyl alcohol has a degree of branching of 1.5 or less.

[0015] (4) In any one of the above (1) to (3), the present invention provides a plasticizer composition in which the isomer mixture of hexyl alcohol contains 1 - hexanol, 2 - methylpentanol, and 3 - methylpentanol.

[0016] (5) In any one of the above (1) to (4), the present invention provides a plasticizer composition in which the isomer mixture of hexyl alcohol contains 40 parts by weight or more of branched - chain alcohol with respect to 100 parts by weight of the isomer mixture.

[0017] (6) In any one of the above (1) to (5), the present invention provides a plasticizer composition in which the isomer mixture of hexyl alcohol contains 50 to 95 parts by weight of branched - chain alcohol with respect to 100 parts by weight of the isomer mixture.

[0018] (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 40 parts by weight or less of 1 - hexanol with respect to 100 parts by weight of the isomer mixture.

[0019] (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 1 - hexanol, 2 - methylpentanol, 3 - methylpentanol, and cyclopentylmethanol.

[0020] (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 20 parts by weight or less of cyclopentylmethanol with respect to 100 parts by weight of the isomer mixture.

[0021] (10) The present invention provides a resin composition containing 100 parts by weight of a resin and 5 to 150 parts by weight of a plasticizer composition according to any one of the above (1) to (9).

[0022] (11) In the present invention as described in (10) above, the resin is one or more resin compositions 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, and synthetic rubbers.

Advantages of the Invention

[0023] When the plasticizer composition according to an embodiment of the present invention is used in a resin composition, it can maintain and improve mechanical properties and stress resistance at an equal or higher level compared to existing plasticizers, and can also improve physical properties such as weight reduction characteristics and plasticization efficiency.

Modes for Carrying Out the Invention

[0024] 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.

[0025] Definition of Terms As used in this specification, the term "composition" includes not only reaction products and decomposition products formed from the materials of the composition, but also mixtures of materials containing the composition.

[0026] As used in this specification, the term "straight vinyl chloride polymer" 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 a size range of several tens to several hundreds of micrometers, and means a polymer having no cohesiveness and excellent fluidity.

[0027] As used herein, the term "paste vinyl chloride polymer" is one type of vinyl chloride polymer and can mean a polymer polymerized by fine suspension polymerization, fine seed polymerization, emulsion polymerization, etc., and means a polymer having cohesiveness and poor fluidity as fine and dense particles having no voids with a size of several tens to several thousands of nanometers.

[0028] The terms "comprising", "having" and their derivatives are not intended to exclude the presence of any additional components, steps or procedures, whether or not they are specifically disclosed. To avoid any ambiguity, all compositions claimed by the use of the term "comprising" can, unless otherwise stated, contain any additional additives, adjuvants or compounds, whether they are polymers or otherwise. In contrast, the term "consisting essentially of" excludes any other components, steps or procedures from the scope of any successive description, except those that are not essential for operation. The term "consisting of" excludes any components, steps or procedures that are not specifically described or listed.

[0029] Measurement Method In this specification, the analysis of the content of components in a composition is carried out 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).

[0030] In this specification, "hardness" means the Shore hardness (Shore "A" and / or Shore "D") at 25°C in accordance with ASTM D2240, measured under the condition of 3T 10s, and can be an index for evaluating the plasticization efficiency. The lower the value, the better the plasticization efficiency.

[0031] In this specification, "tensile strength" is measured using a U.T.M (manufacturer: Instron, model: 4466), which is a test instrument, in accordance with the ASTM D638 method. 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.

[0032] [Mathematical formula 1] Tensile strength (kgf / cm2) = Load value (kgf) / Thickness (cm) × Width (cm)

[0033] In this specification, "elongation rate" is measured using the above U.T.M in accordance with the ASTM D638 method. 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.

[0034] [Mathematical formula 2] Elongation rate (%) = Length after elongation / Initial length × 100

[0035] In this specification, "migration loss" is obtained in accordance with KSM-3156 by obtaining a test piece with a thickness of 2 mm or more, attaching glass plates to both sides of the test piece, and then applying a load of 1 kgf / cm2. 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.

[0036] [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

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

[0038] [Mathematical Formula 4] Volatile loss (%) = { (Weight of the initial test piece) - (Weight of the test piece after working) / (Weight of the initial test piece)} × 100

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

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

[0041] According to an embodiment of the present invention, an aconitate-based composition containing one or more aconitates of the following Chemical Formula 1 is provided, wherein the alkyl group of the aconitate is derived from an isomer mixture of hexyl alcohol, and 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, 3-ethylbutanol, and cyclopentylmethanol.

[0042] [Chemical Formula 1]

Chemical Structure

[0043] In the above Chemical Formula 1, R 1 ~R 3 are each independently an n-hexyl group, a branched hexyl group, or a cyclopentylmethyl group.

[0044] The plasticizer composition can be a product produced by a direct esterification reaction of aconitic acid or its derivative with a mixture of hexyl alcohols, or a transesterification reaction of trialkyl aconitate with a mixture of hexyl alcohols. 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 include two or more selected from the group consisting of 1-hexanol, 1-methylpentanol, 2-methylpentanol, 3-methylpentanol, 4-methylpentanol, 1,1-dimethylbutanol, 1,2-dimethylbutanol, 1,3-dimethylbutanol, 2,2-dimethylbutanol, 2,3-dimethylbutanol, 3,3-dimethylbutanol, 1-ethylbutanol, 2-ethylbutanol, 3-ethylbutanol, and cyclopentylmethanol.

[0045] Depending on the alcohol contained in such hexyl alcohol isomers, the alkyl groups of R 1 ~R 3 in Chemical Formula 1 can be determined. The final composition can include various compositions in which 3, 2, or 1 isomer alkyl groups of hexyl alcohol 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.

[0046] Thus, when applying an aconitate-based plasticizer, when using an alcohol having 6 carbon atoms, the tensile strength, elongation rate, and heat loss can be greatly improved compared to those having less than 6 carbon atoms, and can be excellent in plasticization efficiency compared to those having more than 6 carbon atoms, and can also be excellent in migration resistance, tensile strength, and elongation rate.

[0047] According to one embodiment of the present invention, the hexyl alcohol isomer mixture of the plasticizer composition can have a degree of branching of 2.0 or less, preferably 1.5 or less. Specifically, the degree of branching can be 1.5 or less, can be 1.3 or less, more preferably 1.1 or less, and particularly preferably 1.0 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 aconitate-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 the mechanical properties but also the improvement of migration loss and heat loss can be more optimized, and the balance between physical properties can be excellent.

[0048] 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. In the present invention, the number of branched carbons of 1-hexanol is 0, the number of branched carbons of 1-methylpentanol, 2-methylpentanol, 3-methylpentanol, and 4-methylpentanol is 1, and the number of branched carbons of 1,1-dimethylbutanol, 1,2-dimethylbutanol, 1,3-dimethylbutanol, 2,2-dimethylbutanol, 2,3-dimethylbutanol, 3,3-dimethylbutanol, 1-ethylbutanol, 2-ethylbutanol Of the loop The number of branched carbons is 2.

[0049] The hexyl alcohol isomer mixture can contain 1 - hexanol and 2 - methylpentanol. Thus, when both 1 - hexanol and 2 - methylpentanol are included in the isomer mixture, the balance between physical properties can be maintained, and an excellent effect in terms of weight loss on heating can be obtained. Preferably, it can further contain 3 - methylpentanol. In this case, there is an advantage that the balance between physical properties is very excellent.

[0050] 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 all be 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 included, improvement in mechanical properties can be expected.

[0051] Also, the linear alcohol of 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 can also be absent 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, it is more excellent in the balance of physical properties.

[0052] Further, the isomer mixture of the hexyl alcohol can include 1-hexanol, 2-methylpentanol, 3-methylpentanol, and cyclopentylmethanol. Preferably, by further including cyclopentylmethanol, the plasticization efficiency and the tensile strength can be slightly improved.

[0053] 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 be absent, or the minimum amount for obtaining the effect thereof can be 2 parts by weight.

[0054] Specifically, by characteristics such as the ratio of branched alkyl groups present in the total alkyl groups in the final composition, and further, the ratio of specific branched alkyl groups among the branched alkyl groups, the physical properties of plasticization efficiency and migration / weight loss characteristics can be balanced, and mechanical properties such as tensile strength and elongation, and stress resistance can also be maintained at the same or higher levels, which can be achieved from the components and their component ratios of the isomers of the hexyl alcohol described above.

[0055] Thereby, it is possible to eliminate the environmental problems of existing phthalate-based products and realize products with further improved weight loss characteristics, significantly improve the migration and weight loss characteristics of existing terephthalate-based products, and realize products with improved heat loss compared to existing commercial products.

[0056] 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.

[0057] For example, the composition can be produced by directly esterifying aconitic acid, its anhydride or derivative with the isomer mixture of hexyl alcohol, or the composition can also be produced by transesterifying trialkyl aconitate with the isomer mixture of hexyl alcohol.

[0058] The plasticizer composition according to one 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 aconitates of each type is preferably adjusted, for example, the production method is not particularly limited.

[0059] As an example, the direct esterification reaction includes steps of adding an aconitic acid or its derivative and an isomer mixture of hexyl alcohol, then adding a catalyst and reacting under a nitrogen atmosphere, removing unreacted raw materials, neutralizing (or deactivating) the unreacted raw materials and the catalyst, and removing (e.g., by vacuum distillation) and filtering impurities.

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

[0061] The catalyst can be, for example, one or more selected from acid catalysts such as sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid, p-toluenesulfonic acid, methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, and alkyl 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 suitable.

[0062] The amount of 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 wt%, 0.01 to 3 wt%, 1 to 5 wt%, or 2 to 4 wt% based on the total 100 wt% of the reactants. In the case of a heterogeneous catalyst, it can be in the range of 5 to 200 wt%, 5 to 100 wt%, 20 to 200 wt%, or 20 to 150 wt% of the total amount of the reactants.

[0063] 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.

[0064] As another example, the transesterification reaction can be the reaction of trialkyl aconitate with the isomer mixture of the hexyl alcohol. From the viewpoint of minimizing impurities, the alkyl group of the trialkyl aconitate is preferably a hexyl group. In this case, when the hexyl group of the trialkyl aconitate is linear, the isomer mixture of the hexyl alcohol contains a branched alcohol, or when the hexyl group of the trialkyl aconitate is branched, the isomer mixture of the hexyl alcohol contains a linear alcohol, so that the alkyl group of the finally obtained aconitate contains both linear and branched forms.

[0065] The "transesterification reaction" used in the present invention means a reaction in which an alcohol and an ester react as shown in the following reaction formula 1, and R'' of the ester is mutually exchanged with R' of the alcohol as shown in the following reaction formula 1.

[0066] [Reaction formula 1]

Chemical formula

[0067] 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 the 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.

[0068] However, in the case of the aconitate 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.

[0069] Also, the transesterification reaction has the advantage that it does not cause the problem of wastewater compared to the esterification reaction between an acid and an alcohol.

[0070] The mixture produced by the transesterification reaction can control the composition ratio of the mixture according to the addition amount of 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 aconitate compound. For reference, what determines the component ratio in the final composition can be the addition amount of alcohol as in the direct esterification reaction.

[0071] 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.

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

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

[0074] 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 of these.

[0075] In addition, after the transesterification reaction, a step of distilling and removing unreacted alcohol and reaction by-products, etc. 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 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.

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

[0077] 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.

[0078] The plasticizer composition can be contained in an amount of 5 to 150 parts by weight, preferably 5 to 130 parts by weight, or 10 to 120 parts by weight based on 100 parts by weight of the resin.

[0079] Generally, the resin in which the plasticizer composition is used can be manufactured as a resin product by melt processing or plastisol processing, and the melt-processed resin and the plastisol-processed resin can be produced to be different according to each polymerization method.

[0080] 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.

[0081] 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.

[0082] 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.

[0083] 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.

[0084] In addition, the resin composition can further contain other additives such as stabilizers as necessary. 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.

[0085] As the stabilizer, for example, a calcium-zinc (Ca-Zn) stabilizer or a barium-zinc (Ba-Zn) stabilizer such as a calcium-zinc composite stearate can be used, but it is not particularly limited thereto.

[0086] As described above, the resin composition is applicable to both melt processing and plastisol processing. For example, melt processing can be applied to calendering, extrusion, or injection molding, and plastisol processing can be applied to coating or the like.

[0087] Examples 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 modified into various other forms, and the scope of the present invention should not be construed as being limited to the examples detailed below. The examples of the present invention are provided to more fully explain the present invention to those with average knowledge in the industry.

[0088] Example 1 To 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 hexyl alcohol, and 1.5 g of tetrabutyl titanate (TnBT) were added. After that, 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.

[0089] 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.

[0090] Example 2 The procedure was the same as in Example 1 above, but as the isomer mixture of hexyl alcohol, a mixture of 1-hexanol, 2-methylpentanol, and 3-methylpentanol in a weight ratio of 20:35:45 was used to obtain a plasticizer composition.

[0091] Example 3 The procedure was the same as in Example 1 above, but as the isomer mixture of hexyl alcohol, a mixture of 1-hexanol, 2-methylpentanol, 3-methylpentanol, and cyclopentylmethanol in a weight ratio of 10:45:30:15 was used to obtain a plasticizer composition.

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

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

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

[0095] Comparative Example 4 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.

[0096] Comparative Example 5 In the said comparative example 4 A plasticizer composition was obtained in the same manner as in Example 1, except that acetic anhydride was added for acetylation after the esterification reaction.

[0097] Comparative Example 6 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 hexyl alcohol in Example 1.

[0098] Comparative Example 7 A plasticizer composition was obtained in the same manner as in Example 1, except that 680 g of n-pentanol single compound was used instead of the isomer mixture of hexyl alcohol in Example 1.

[0099] Comparative Example 8 A plasticizer composition was obtained in the same manner as in Example 1, except that 890 g of n-heptanol single compound was used instead of the isomer mixture of hexyl alcohol in Example 1.

[0100] The types of acids and alcohols used in the said examples and comparative examples were summarized and shown in Table 1 below.

[0101]

Table 1

[0102] Experimental Example 1: Evaluation of Sheet Performance Using the plasticizers of the examples and comparative examples, test pieces were prepared according to ASTM D638 under the following formulations and production conditions.

[0103] (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)

[0104] (2) Blending: Mixing at 98 °C at 700 rpm

[0105] (3) Preparation of test pieces: Working with a roll mill at 160 °C for 4 minutes and with a press at 180 °C for 2.5 minutes (low pressure) and 2 minutes (high pressure) to prepare 1T, 2T, and 3T sheets

[0106] (4) Evaluation items 1) Hardness : According to ASTM D2240, the Shore hardness at 25 °C (Shore "A" and "D") was measured for 10 seconds on a 3T test piece. The smaller the value, the better the plasticization efficiency is evaluated.

[0107] 2) Tensile Strength and Tensile Strength Retention : According to the method of ASTM D638, using a U.T.M (manufacturer; Instron, model; 4466) as a test instrument, after pulling at a cross head speed of 200 mm / min, the point where the 1T test piece was cut was measured. The tensile strength was calculated as follows.

[0108] Tensile strength (kgf / cm 2 ) = Load value (kgf) / Thickness (cm) × Width (cm)

[0109] The tensile retention rate measures the ratio of the tensile strength 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 of the above-mentioned tensile strength.

[0110] 3) Measurement of Tensile Elongation and Tensile Elongation Retention: According to the method of ASTM D638, using the U.T.M, after pulling at a cross head speed of 200 mm / min, the point where the 1T test piece was cut was measured, and then the elongation rate was calculated as follows.

[0111] Elongation rate (%) = (Length after elongation / Initial length) × 100 was calculated.

[0112] The remaining elongation 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 of the above-mentioned elongation rate.

[0113] 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

[0114] 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.

[0115] Loss on heating (weight %) = (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 was calculated.

[0116] 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 (bleeding degree) was observed, and the result was described numerically. The closer to 0, the better the characteristics were shown.

[0117] 7) Absorption Rate Evaluation : During the compounding process of the plasticizer and the resin composition, the time until the torque of the mixer stabilizes was measured and evaluated.

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

[0119] [Table 2]

[0120] [Table 3]

[0121] Referring to Tables 2 and 3 above, in the case of Examples 1 to 3 to which the plasticizer composition according to an embodiment of the present invention was applied, compared with Comparative Example 1 which was conventionally known as a typical phthalate plasticizer, similar plasticizing efficiency, migration property and heat loss were shown, and it was shown that the tensile strength and elongation rate were improved instead. Further, compared with Comparative Example 2 which is another phthalate plasticizer, similar results were shown in terms of migration property and mechanical properties, and improved results were shown in terms of plasticizing efficiency and absorption rate. The aconitate plasticizer of the present invention is different from the existing phthalate plasticizers. Considering the environmental friendliness, it can be confirmed from the above results that the aconitate plasticizer of the present invention can sufficiently replace the existing phthalate plasticizer products and be used.

[0122] Also, in the case of Comparative Example 3 which is a commercially available terephthalate plasticizer product for replacing the phthalate plasticizers of Comparative Examples 1 and 2, the migration loss and stress resistance were much inferior compared to the examples of the present invention, and it was also inferior in terms of plasticizing efficiency and absorption rate.

[0123] On the one hand, Comparative Examples 4 and 5 applied an isomer mixture of hexyl alcohol, similar to Examples 1 to 3 of the present invention, but applied citric acid or acetylcitric acid instead of aconitic acid. In the case of Comparative Example 4 using citric acid, both the tensile properties and elongation properties were inferior to those of the examples. In the case of Comparative Example 5 using citric acid and additionally acetylating it, it was inferior to the examples in terms of plasticization efficiency, elongation properties, migration properties, stress resistance, and absorption rate. That is, it was confirmed from this that the improved physical properties of the present invention can be achieved only when aconitic acid is applied as the carboxylic acid.

[0124] Further, Comparative Example 6 used a single 2-methylpentanol instead of the isomer mixture of hexyl alcohol used in the present invention, and was inferior in terms of tensile strength and elongation rate compared to the examples. From this, it was confirmed that when applying an isomer mixture of hexyl alcohol instead of a single alcohol, an improvement in the effect in terms of mechanical physical properties can be achieved.

[0125] Finally, in the case of Comparative Example 7 using an alcohol having 5 carbon atoms instead of the isomer mixture of hexyl alcohol used in the present invention, the tensile properties and elongation properties were significantly inferior to those of the examples, and were also significantly inferior to the examples in terms of weight loss on heating and stress resistance. In the case of Comparative Example 8 using an alcohol having 7 carbon atoms, the plasticization efficiency was inferior to that of the examples. Similarly, it was inferior to the examples in terms of tensile properties and elongation properties, and all of the migration properties, stress resistance, and absorption rate were inferior to those of the examples.

[0126] Thus, when applying the esterification reactant of the isomer mixture of aconitic acid and hexyl alcohol as a plasticizer as in the embodiments of the present invention, existing products can be fully replaced, and a plasticizer with excellent performance can be realized. In particular, by selecting and applying the acid and alcohol, which are the isomer mixture of aconitic acid and hexyl alcohol, it was confirmed that a plasticizer composition with excellent balance among various physical properties and excellent overall physical properties can be provided.

Claims

1. An aconitate-based composition containing one or more aconitates of the following Chemical Formula 1, wherein the alkyl group of the aconitate is derived from an isomer mixture of hexyl alcohol, and the isomer mixture of hexyl alcohol contains 1-hexanol, 2-methylpentanol, and 3-methylpentanol, an aconitate-based plasticizer composition. [Chemical Formula 1] 【Chemical 1】 In the above Chemical Formula 1, R １ to R ３ are each independently an n-hexyl group, a branched hexyl group or a cyclopentylmethyl group.

2. The plasticizer composition according to Claim 1, wherein the isomer mixture of hexyl alcohol has a branching degree of 2.0 or less.

3. The plasticizer composition according to Claim 2, wherein the isomer mixture of hexyl alcohol has a branching degree of 1.5 or less.

4. 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.

5. 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.

6. 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.

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

8. The plasticizer composition according to Claim 7, 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.

9. A resin composition containing 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 is one or more 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. The resin composition according to Claim 9.

Images