Ester-based plasticizer composition and its use

Abstract

The present invention relates to an ester-based plasticizer composition and its use, which can provide a synergistic effect in improving thermal stability such as migration resistance and heat loss, and can help improve the physical properties of molded products. It can provide molded products that are excellent in compatibility with polyvinyl chloride resins and processability, and that are excellent in mechanical properties as well as thermal stability.

Description

[Technical field]

[0001] The present invention relates to an ester plasticizer composition and its use. [Background technology]

[0002] Polymer resins used in daily life are applied and used in various fields such as household and home appliances, clothing, automobiles, construction materials, and packaging materials according to their respective characteristics. In general, polymer resins selected from polyethylene (PE), polypropylene (PP), polystyrene (PS), polyurethane (PU), polyvinyl chloride (PVC), etc. are widely used. In particular, polyvinyl chloride has hard and soft characteristics, can be advantageously applied to various molding methods, is highly cost competitive, and has versatile utility, so it is used in various fields from household goods to industrial materials.

[0003] Such polyvinyl chloride is used with the addition of a plasticizer to achieve various physical properties, rather than being used as a resin alone. The plasticizer serves to impart flexibility to the resin and improve physical properties such as processability and moldability. However, with the development of industry, the role of the plasticizer has diversified to enhance not only flexibility but also properties required according to the field of application, such as volatility resistance, migration resistance, aging resistance, cold resistance, oil resistance, water resistance, and heat resistance.

[0004] Examples of ester compounds commonly used as plasticizers include di-(2-ethylhexyl)phthalate (DEHP), di-isononyl phthalate (DINP), di-2-propylheptyl phthalate (DPHP), and diisodecyl phthalate (DIDP). However, these are phthalate plasticizers, and their use tends to be restricted due to the problem of environmental hormones. In addition, dioctyl terephthalate (DOTP), a representative non-phthalate plasticizer, has limitations in terms of thermal stability such as migration and volatility (heat loss), and thus the improvement of product properties.

[0005] Therefore, there is still a need for research to provide a plasticizer that can solve the problems of ester-based compounds conventionally used as plasticizers and can sufficiently improve the physical properties of existing products in various aspects, including processability with polyvinyl chloride resin. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] KR10-2008-0105341A Summary of the Invention [Problem to be solved by the invention]

[0007] An object of the present invention is to provide an ester-based plasticizer composition having improved thermal stability and uses thereof.

[0008] In detail, the object is to provide an ester-based plasticizer composition having improved thermal stability such as migration resistance and heat loss and excellent compatibility, a polyvinyl chloride resin composition containing the same, and a molded article produced from the same.

[0009] In detail, the object is to provide an ester-based plasticizer composition which can realize excellent tensile strength, elongation and hardness as well as improve thermal stability, and can impart aging resistance to these physical properties, a polyvinyl chloride resin composition containing the same, and a molded article produced from the same. [Means for solving the problem]

[0010] In order to solve the above problems, the present invention provides an ester-based plasticizer composition represented by the following Chemical Formula 1, which satisfies the following Relational Formula 1. [ka] [In the above Chemical Formula 1, n is an integer from 0 to 10, R 1 and R2 are each independently 4-15 is alkyl, L 1 and L 2 are each independently ethylene or propylene. [Equation 1] 0.05≦|(A 0 -A 1~3 ) / A n |≦0.45 [In the above-mentioned Relational Formula 1, A n is 100% by weight of the total weight of the ester-based plasticizer composition, A 0 is the weight percent of the compound of Chemical Formula 1 where n=0; A 1~3 is the weight percent of the mixture in Chemical Formula 1 where n is 1 to 3.]

[0011] The ester-based plasticizer composition according to one embodiment of the present invention can satisfy the following Relation 2. [Equation 2] 0≦A 4~10 / A 1~3 ≦0.2 [In the above-mentioned Relational Formula 2, Relative to the total weight of the ester plasticizer composition, A 1~3 is the weight percent of the mixture of Chemical Formula 1 where n=1 to 3; A 4~10 is the weight percent of the mixture in Chemical Formula 1 where n is 4 to 10.]

[0012] The ester-based plasticizer composition according to one embodiment of the present invention contains, based on the total weight, 0 can be in the range of 30 to 80% by weight.

[0013] In the ester-based plasticizer composition according to an embodiment of the present invention, the R 1 and R 2 are each independently 7-13 It can be a branched alkyl.

[0014] In the ester-based plasticizer composition according to an embodiment of the present invention, the R 1 and R 2 are each independently 4-6 It can be a straight chain alkyl.

[0015] The present invention also provides a polyvinyl chloride resin composition comprising the above-mentioned ester-based plasticizer composition.

[0016] The polyvinyl chloride resin composition according to one embodiment of the present invention may contain 5 to 100 parts by weight of the ester-based plasticizer composition based on 100 parts by weight of the polyvinyl chloride resin.

[0017] The polyvinyl chloride resin composition according to one embodiment of the present invention may further include a heat stabilizer, a filler, or a combination thereof.

[0018] The present invention also provides a molded article produced from the above-mentioned polyvinyl chloride resin composition.

[0019] Furthermore, the molded article according to an embodiment of the present invention may be a wire covering material, a floor material, an automobile interior material, a film, a sheet, a wallpaper, a tube, or the like. Effect of the Invention

[0020] According to the present invention, it is possible to provide an ester-based plasticizer composition containing two or more ester compounds, which can fully satisfy the physical properties such as heat resistance and compatibility required for heat-resistant resin compositions such as polyvinyl chloride resins. In particular, the ester-based plasticizer composition according to the present invention is noteworthy in that it can overcome the limitations of conventional plasticizers that are widely used as plasticizers because it satisfies a specific relational formula.

[0021] The present invention is particularly excellent in terms of thermal stability properties such as migration resistance and heat loss. Due to such synergistic effect, the present invention can improve compatibility, i.e., plasticization efficiency, and is more useful for improving the physical properties of molded products. Furthermore, the ester-based plasticizer composition of the present invention can provide molded products with excellent mechanical properties by combining with polyvinyl chloride resin. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0022] Hereinafter, the ester-based plasticizer composition and its use according to the present invention will be described in detail. Unless otherwise defined, the technical and scientific terms used herein have the meanings that are commonly understood by those having ordinary knowledge in the technical field to which the present invention belongs, and the following description and the accompanying drawings omit the description of known functions and configurations that may obscure the gist of the present invention.

[0023] As used herein, the singular forms "a," "an," and "the" can be intended to include the plural forms as well, unless the context indicates otherwise.

[0024] Furthermore, units used in this specification without any special mention are based on weight, and as an example, a unit of % or ratio means % by weight or weight ratio, and % by weight means the weight % that any one component of the entire composition occupies in the composition, unless otherwise defined.

[0025] In addition, the numerical ranges used herein include lower and upper limits and all values ​​within the range, increments logically derived from the form and width of the ranges defined, all values ​​that are doubly limited, and all possible combinations of upper and lower limits of numerical ranges that are limited in different forms. Unless otherwise specified in the specification of the present invention, values ​​outside the numerical ranges that may occur due to experimental error or rounding of values ​​are also included in the defined numerical ranges.

[0026] As used herein, the term "comprising" is an open-ended term having the same meaning as expressions such as "comprising," "containing," "having," or "characterized by," and does not exclude further unrecited elements, materials, or steps.

[0027] As used herein, the term "alkyl" refers to a monovalent radical derived from an aliphatic hydrocarbon of straight or branched chain configuration. Also, "ethylene" refers to the -CH 2 CH 2 -, and "propylene" has the structural formula -CH 2 CH 2 CH 2 -or-CH(CH 3 )CH 2 -

[0028] Plasticizer migration refers to the phenomenon in which a part of a plasticizer mixed with a heat-resistant resin leaks out of the heat-resistant resin. In the case of some phthalate plasticizers among conventional plasticizers, if the leaked plasticizer enters the body, it can inhibit the normal activity of the endocrine system, which is directly involved in vital activities, or cause abnormal reactions that can cause fatal damage, so it was necessary to suppress plasticizer migration as much as possible. On the other hand, conventional non-phthalate plasticizers, which are commonly known, do not enter the body and cause problems for the endocrine system, but they have low thermal stability, making it impossible to solve the problem of plasticizer migration.

[0029] Therefore, the present inventors have conducted extensive research into plasticizers that can effectively suppress plasticizer migration, as well as processability with heat-resistant resins such as polyvinyl chloride resin, and have devised an ester-based plasticizer composition having ester groups derived from alcohols with different structural characteristics. The present inventors have found that the ester-based plasticizer composition of the present invention can improve thermal stability such as heat loss, as well as plasticizer migration, which has been pointed out as a limitation of conventional plasticizers, by adjusting the ratio of repeating units, and have completed the present invention.

[0030] The present invention will be specifically described below.

[0031] The present invention provides an ester-based plasticizer composition represented by the following Chemical Formula 1, which satisfies the following Relational Formula 1:

[0032] [ka]

[0033] [In the above Chemical Formula 1, n is an integer from 0 to 10, R 1 and R 2 are each independently 4-15 is alkyl, L 1 and L 2 are each independently ethylene or propylene.

[0034] [Equation 1] 0.05≦|(A 0 -A 1~3 ) / A n |≦0.45

[0035] [In the above-mentioned Relational Formula 1, A n is 100% by weight of the total weight of the ester-based plasticizer composition, A 0 is the weight percent of the compound of Chemical Formula 1 where n=0; A 1~3 is the weight percent of the mixture in Chemical Formula 1 where n is 1 to 3.]

[0036] The ester plasticizer composition according to one embodiment of the present invention satisfies the above-mentioned relational formula 1, and is excellent in properties such as heat loss as well as migration resistance, and does not cause any inconvenience in mechanical properties such as hardness, elongation, and tensile strength of the heat-resistant resin in which it is used. In addition, despite containing a polymeric ester compound, it has improved plasticizing efficiency and is also excellent in compatibility with heat-resistant resins such as polyvinyl chloride resin. On the other hand, if the above-mentioned relational formula 1 is not satisfied, it is difficult to simultaneously achieve improved migration and heat loss.

[0037] In the ester-based plasticizer composition according to one embodiment of the present invention, the relational expression 1 may be greater than 0.05, preferably 0.07 or more, more preferably 0.08 or more, and most preferably 0.09 or more and less than 0.45.

[0038] At the same time, the ester-based plasticizer composition according to one embodiment of the present invention can satisfy the following Relation 2.

[0039] [Equation 2] 0≦A 4~10 / A 1~3 ≦0.2

[0040] [In the above-mentioned Relational Formula 2, Relative to the total weight of the ester plasticizer composition, A 1~3 is the weight percent of the mixture of Chemical Formula 1 where n=1 to 3; A 4~10 is the weight percent of the mixture in Chemical Formula 1 where n is 4 to 10.]

[0041] Such formulas 1 and 2 are represented by the following formulas: 2-3 The amount of polyalkylene glycol used, i.e., the ratio thereof, can be appropriately adjusted. When the ester-based plasticizer composition according to one embodiment of the present invention satisfies the above-mentioned Relational Formula 1 and Relational Formula 2, the interaction between the ester-based compounds in the composition can provide a synergistic effect to the intended effect.

[0042] Specifically, by mixing the above-mentioned components in the composition, the ester-based plasticizer composition of the present invention can balance physical properties such as migration and heat loss, and can improve mechanical properties such as tensile strength and elongation. In addition, the interaction between these properties can significantly improve aging resistance. In other words, the ester-based plasticizer composition of the present invention that satisfies the above-mentioned formula can provide a plasticizer composition that eliminates the environmental problems of conventional phthalate-based plasticizers and further improves migration and heat loss.

[0043] The ester-based plasticizer composition according to one embodiment of the present invention contains, based on the total weight, 0 In addition, in terms of showing a synergistic effect that is further improved in terms of migration, 0 can be in the range of more than 30% by weight and less than 80% by weight. It can also be in the range of 31 to 78% by weight, or 31 to 75% by weight.

[0044] For example, the ester-based plasticizer composition may be a mixture of ester-based compounds in which n in Formula 1 satisfies 0 to 8.

[0045] For example, the ester-based plasticizer composition may be a mixture of ester-based compounds in which n in Formula 1 satisfies 0 to 6.

[0046] For example, the ester-based plasticizer composition may be a mixture of ester-based compounds in which n in Chemical Formula 1 satisfies 0 to 5. Here, the ester-based plasticizer composition may contain 5 to 40 wt % of an ester-based compound having two or more cyclic groups.

[0047] In the ester-based plasticizer composition according to an embodiment of the present invention, the R 1 and R 2 are each independently 7-13 It can be a branched alkyl, preferably C 8-13 It can be a branched alkyl, more preferably C 8-10 It can be a branched alkyl.

[0048] As an example, the R 1 and R 2 can each independently be part of an ester group derived from a monohydric fatty alcohol, such as 2-ethylhexanol, isononyl alcohol, isodecyl alcohol, 2-propylheptanol, or isotridecyl alcohol.

[0049] In the ester-based plasticizer composition according to an embodiment of the present invention, the R 1 and R 2 are each independently 4-6 It can be a straight chain alkyl, preferably C 4-5 It can be a straight chain alkyl.

[0050] As an example, the R 1 and R 2 can be a substituent derived from n-butanol, and the like.

[0051] For example, the ester-based plasticizer composition may contain a polymeric ester-based plasticizer having a weight-average molecular weight of 1000 g / mol or more, and may contain the polymeric ester-based plasticizer in an amount of 10 wt% or less, 9.5 wt% or less, or 0 to less than 9.5 wt% based on the total weight.

[0052] For example, the ester-based plasticizer composition may contain a low molecular weight ester-based plasticizer having a weight average molecular weight of less than 1000 g / mol, and may contain the low molecular weight ester-based plasticizer in an amount of 80 wt % or more based on the total weight.

[0053] According to one embodiment of the present invention, non-phthalate plasticizers, which are one of the commonly known plasticizers, have relatively high migration properties compared to the phthalate plasticizers, and thus have limited application fields. However, the ester plasticizer composition according to the present invention is noteworthy in that it can significantly improve thermal stability such as heat loss, not to mention migration resistance, and that such effects are more prominent than those of a single compound or a compound that does not satisfy the above-mentioned relationship.

[0054] The ester-based plasticizer composition according to the embodiment of the present invention is a compound represented by the following formula 2 and C 2-3 It can be produced by a step of subjecting a polyalkylene glycol to a transesterification reaction in the presence of a catalyst.

[0055] [ka]

[0056] [In the above Chemical Formula 2, R 1 and R 2 are each independently 4-15 is alkyl.

[0057] The transesterification reaction is 2-3 The polyalkylene glycol and the compound represented by the formula 2 react with each other to exchange the substituents. 2-3 The alkoxide of polyalkylene glycol attacks the carbon of the ester group of two molecules of Chemical Formula 2, respectively, to form the compound of Chemical Formula 1. In addition, the compound of Chemical Formula 2 may remain as an unreacted portion that has not undergone reaction.

[0058] In the method for preparing an ester-based plasticizer composition according to one embodiment of the present invention, the above steps may be carried out in the presence of an organometallic catalyst including Sn or Ti, an acid catalyst including sulfonic acid or sulfuric acid, or a mixture of these. The amount of the catalyst used is not limited, and may be a normal catalyst amount. In addition, when an organometallic catalyst including Zn is used in the above steps, the desired relationship in the present invention cannot be satisfied due to low reaction efficiency, which is not preferable.

[0059] As an example, in the organometallic catalyst, the Ti-based organometallic catalyst can be selected from tetraalkyl titanates such as tetramethyl titanate, tetraethyl titanate, tetrapropyl titanate, tetra-isopropyl titanate, tetrabutyl titanate, tetrapentyl titanate, tetrahexyl titanate, tetra-octyl titanate, tetranonyl titanate, tetradodecyl titanate, tetrahexadecyl titanate, tetra-octadecyl titanate, tetradecyl titanate and tetraheptyl titanate; and tetraaryl titanates such as tetraphenyl titanate.

[0060] As an example, the acid catalyst may be selected from sulfuric acid, paratoluenesulfonic acid, methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, and the like.

[0061] For example, the catalyst can be used in a normal amount, and specifically, it is preferable to use 0.01 to 1 part by weight, or 0.01 to 0.5 parts by weight, or 0.02 to 0.1 parts by weight, relative to 100 parts by weight of the total weight of the compound represented by Chemical Formula 2, but the amount is not limited thereto.

[0062] Moreover, the transesterification reaction has an advantage over the esterification reaction between an acid and an alcohol in that it does not cause a wastewater problem, and can be carried out in the absence of a catalyst.

[0063] The ester plasticizer composition according to the present invention produced by the above-mentioned production method can realize a synergistic effect that is surprisingly improved in terms of migration resistance and volatility resistance. This synergistic effect is expected to be due to the fact that the plasticizer does not leak out of the vinyl chloride resin due to interactions such as hydrogen bonds between the ester group of Chemical Formula 1 and the ester group of Chemical Formula 2, but the synergistic effect of the ester plasticizer composition according to the present invention does not depend on this characteristic. Furthermore, the ester plasticizer composition according to the present invention exhibits excellent migration resistance because it satisfies the above-mentioned relationship.

[0064] In the method for preparing an ester-based plasticizer composition according to an embodiment of the present invention, the transesterification reaction may be initiated at a reaction temperature of 80° C. or higher.

[0065] As an example, the reaction temperature of the above step can be 135° C. or higher.

[0066] As an example, the reaction temperature of the above step can be 150° C. or higher.

[0067] As an example, the reaction temperature in the above step may be 170 to 270°C.

[0068] As an example, the step may be carried out at the above reaction temperature for 10 minutes to 24 hours, and it goes without saying that the reaction time may be appropriately adjusted depending on the purpose. The reaction time may be appropriately adjusted via the acid value obtained by the following formula 1. The lower the acid value, the more preferable, but it is not limited as long as it is a value of 5 or less. Here, a high acid value means that unreacted aromatic compounds remain in the plasticizer, which may adversely affect the purity of the plasticizer.

[0069] [Formula 1] Acid value = (titer amount x 5.6 x factor) / sample amount

[0070] [In the above formula 1, If the alkaline solution used in the titration is 0.1N KOH aqueous solution, the factor is 1.

[0071] The steps may also be performed under an inert atmosphere, which refers to an inert gas atmosphere selected from nitrogen, argon, and the like.

[0072] The method for producing an ester-based plasticizer composition according to an embodiment of the present invention may further include a purification step, which includes recovering unreacted alcohol, reaction by-products, or the like, after the above steps. The unreacted alcohol recovered through such a purification step can be reused and thus can be used continuously in the reaction step, which provides an advantage in that a more economical process can be provided. Here, the unreacted alcohol is C 2-3 It may refer to a polyalkylene glycol.

[0073] The neutralizing step can be carried out using a conventional alkaline solution.

[0074] The step of recovering the unreacted alcohol may be a step of removing alcohol that is a reaction by-product, not to mention unreacted alcohol, and may be a distillation step using the difference in boiling points. When undergoing such a distillation step, it is preferable that the difference in boiling points of the substances to be separated is preferably 10°C or more. In addition, the distillation may be a multi-stage distillation or a mixed distillation. In the case of the multi-stage distillation, it may be a method of separately separating the substances to be separated according to the difference in boiling points of each substance, and in the case of the mixed distillation, it may be a method of simultaneously distilling the substances to be separated.

[0075] Specifically, in the method for producing an ester-based plasticizer composition according to an embodiment of the present invention, the C 2-3 The polyalkylene glycol may be contained in an amount of 0.1 to 5 mol, or 0.3 to 3 mol, or 0.5 to 1.5 mol.

[0076] According to the above-mentioned method for producing an ester-based plasticizer composition of the present invention, the molecular weight of the plasticizer is improved and the number of functional groups capable of interacting with resin, i.e., ester groups, is increased. Generally, the aging resistance of a plasticizer depends on its molecular weight, structural characteristics, etc., and the larger the molecular weight of the plasticizer, the better the aging resistance, but the lower the compatibility with resin tends to be. However, according to the present invention, not only the aging resistance but also the compatibility with resin can be improved at the same time, which is different from the tendency of the prior art.

[0077] By using the above-mentioned production method, the ratio of each repeating unit can be adjusted to satisfy the above-mentioned Relational Formula 1 and Relational Formula 2, thereby producing the intended ester-based plasticizer composition of the present invention. It goes without saying that the ratio of each component can be adjusted, and the conditions for adding each component can also be adjusted to satisfy the above-mentioned Relational Formula 1 and Relational Formula 2.

[0078] An ester-based plasticizer composition according to one embodiment of the present invention may be prepared by hydrogenating a compound represented by the following Formula 3 having a terephthalate basic structure.

[0079] [ka]

[0080] [In the above Chemical Formula 3, n is an integer from 0 to 10, R 1 and R 2 are each independently 4-15 is alkyl, L 1 and L 2 are each independently ethylene or propylene.

[0081] The hydrogenation reaction may be carried out in the presence of a metal catalyst, which may be a type of reduction reaction. The metal catalyst may be any catalyst capable of hydrogenation, and non-limiting examples thereof include Rh / C catalyst, Pt catalyst, Pd catalyst, etc.

[0082] According to the above-mentioned method for producing an ester-based plasticizer composition of the present invention, the weight average molecular weight of the plasticizer composition can be improved, and the number of functional groups capable of interacting with heat-resistant resins, i.e., ester-based compounds with an increased number of ester groups and their compositions can be adjusted. In general, the aging resistance of plasticizers is influenced by their molecular weight, structural characteristics, etc., and the larger the molecular weight of the plasticizer, the better the aging resistance, but the lower the compatibility with heat-resistant resins. However, according to the present invention, the aging resistance as well as the compatibility with heat-resistant resins can be improved at the same time due to these interactions within the composition, which is different from the prior art.

[0083] In addition, the ester-based plasticizer composition prepared by the preparation method according to one embodiment of the present invention is an ester-based plasticizer composition of Formula 1 that satisfies Relation 1, and is a mixture of at least two ester compounds represented by Formula 1. Due to this composition, the ester-based plasticizer composition according to the present invention exhibits excellent synergistic effects in terms of migration resistance and volatility resistance.

[0084] The ester-based plasticizer composition produced by the production method according to one embodiment of the present invention may contain 30 to 75 wt %, preferably more than 30 wt %, more preferably in the range of 31 to 65 wt %, of the compound of Chemical Formula 1, where n = 0. In particular, when the compound of Chemical Formula 1, where n = 0, is contained in the range of 31 to 60 wt %, the composition may exhibit significantly reduced migration.

[0085] Meanwhile, in the ester-based plasticizer composition prepared by the method of the present invention, when the compound of Formula 1, n=0, is contained in an amount of more than 55 wt %, the elongation before heating may be more preferable.

[0086] The ester-based plasticizer composition according to one embodiment of the present invention contains a conventional plasticizer, i.e., a plasticizer such as cyclohexane diester (DEHCH), and can achieve improved migration, volatility (heat loss), etc. Also, it provides an excellent advantage in terms of volatility of the test specimens produced therefrom. As a result, the ester-based plasticizer composition according to the present invention is preferable because it can provide excellent physical properties as a plasticizer.

[0087] That is, the ester-based plasticizer composition according to one embodiment of the present invention can solve the problems of the low molecular weight plasticizers described above, as well as the problems of the existing polymer-based plasticizers. Specifically, the ether-based plasticizer composition according to the present invention can achieve a hardness equivalent to that of the low molecular weight plasticizers described above, with improved plasticizing efficiency, despite containing a polymer-based ether compound having a weight-average molecular weight of 1000 or more. This does not cause any inconvenience in processability with heat-resistant resins such as polyvinyl chloride resin, and can help improve the physical properties of molded products produced therefrom with high plasticizing efficiency.

[0088] The present invention also provides a polyvinyl chloride resin composition containing the above-mentioned ester-based plasticizer composition and a molded article produced therefrom.

[0089] As described above, according to the present invention, it is possible to provide a molded product having improved migration resistance and heat loss, as well as excellent tensile strength, elongation, and aging resistance (e.g., rate of change in tensile strength, rate of change in elongation after heating, etc.).

[0090] The polyvinyl chloride resin may be a vinyl chloride monomer alone or a copolymer of a vinyl chloride monomer and a comonomer copolymerizable therewith, or may be a copolymer prepared by a polymerization method such as suspension polymerization, microsuspension polymerization, emulsion polymerization, or miniemulsion polymerization by mixing a suspending agent, a buffering agent, and a polymerization initiator.

[0091] Other monomers that can be copolymerized with the vinyl chloride monomer described above can be used without any restrictions if they are ordinary monomers, and non-limiting examples thereof include vinyl ester monomers including ethylene vinyl acetate monomer and vinyl propionate monomer; olefin monomers including ethylene, propylene, isobutyl vinyl ether, and halogenated olefin; methacrylic acid ester monomers including alkyl methacrylate ester; maleic anhydride monomer; acrylonitrile monomer; styrene monomer; and halogenated polyvinylidene; and the like, and one or more of these can be mixed to produce a copolymer with vinyl chloride monomer. However, the present invention is not limited to the above-mentioned monomers, and monomers that are generally used to form a copolymer by polymerization reaction with vinyl chloride monomer in the technical field to which the present invention belongs can be used without any particular restrictions depending on the physical properties and applications of the vinyl chloride resin composition required during production.

[0092] In the polyvinyl chloride resin composition according to one embodiment of the present invention, the polyvinyl chloride resin may have a degree of polymerization of 300 to 3,000, preferably 500 to 2,000, and more preferably 700 to 1,200.

[0093] In the polyvinyl chloride resin composition according to one embodiment of the present invention, the ester-based plasticizer composition may be included in an amount of 5 to 100 parts by weight, specifically 10 to 80 parts by weight, and more specifically 30 to 60 parts by weight, based on 100 parts by weight of the polyvinyl chloride resin.

[0094] In addition, the polyvinyl chloride resin composition according to one embodiment of the present invention may further include an additive selected from a heat stabilizer, a filler, and the like.

[0095] For example, the heat stabilizer may be a composite heat stabilizer including two or more selected from Ca, Zn, Al, Mg, and the like.

[0096] For example, the heat stabilizer may be included in an amount of 1 to 15 parts by weight based on 100 parts by weight of the polyvinyl chloride resin. Specifically, the heat stabilizer may be included in an amount of 3 to 12 parts by weight, more specifically, 5 to 10 parts by weight. When used in the above amount, it helps to improve the heat stability. In addition, since it has excellent compatibility and synergistic effect with the ester-based plasticizer composition according to the present invention and the polyvinyl chloride resin, it shows an effect superior to other stabilizers. In addition, a non-metallic stabilizer selected from benzophenol, triazole, acrylonitrile, etc. may be further included.

[0097] For example, the filler can improve the productivity and dry touch of the polyvinyl chloride resin composition, and can be selected from calcium carbonate, clay, talc, diatomaceous earth, etc.

[0098] For example, the filler may be contained in an amount of 1 to 100 parts by weight, specifically 5 to 50 parts by weight, more specifically 5 to 30 parts by weight, based on 100 parts by weight of the polyvinyl chloride resin. Needless to say, the filler may be used in an amount of more than 100 parts by weight based on 100 parts by weight of the polyvinyl chloride resin, depending on the purpose.

[0099] The polyvinyl chloride resin composition according to one embodiment of the present invention has a high absorption rate and a short melting time for polyvinyl chloride resin, and enhances processability with polyvinyl chloride resin. In addition, the polyvinyl chloride resin composition according to the present invention may contain a heat-resistant resin selected from the group consisting of polyvinyl chloride resin, acrylic resin, ABS resin, urethane resin, and polyester resin, and may also contain various other polymer resins.

[0100] The polyvinyl chloride resin composition according to one embodiment of the present invention may be applied to various types of formulations depending on the purpose, and non-limiting examples thereof include a compound formulation, a sheet formulation, and a plastisol formulation.

[0101] It goes without saying that the molded article produced from the above-mentioned polyvinyl chloride resin composition can be used in various forms depending on the purpose and shape. Specifically, the molded article can be a wire covering material, etc. It can also be used as a flooring material, an automobile interior material, a film, a sheet, a wallpaper, or a tube.

[0102] As described above, the present invention provides a molded product having particularly low heat loss and migration resistance, wherein the migration resistance and heat loss are measured by the following evaluation methods.

[0103] As an example, a molding according to the present invention may have a migration resistance of 0.2% or less.

[0104] As an example, a molding according to the present invention may have a migration resistance of 0.15% or less.

[0105] As an example, the molded product according to the present invention may have a migration resistance of 0.01 to 0.1%.

[0106] As an example, the molded product according to the present invention may have a migration resistance of 0.03 to 0.08%.

[0107] As an example, the molded product according to the present invention has a heat loss (W1 ) may be 1.0% or less.

[0108] As an example, the molded product according to the present invention has a heat loss (W 1 ) may be 0.9% or less.

[0109] As an example, the molded product according to the present invention has a heat loss (W 1 ) may be 0.1 to 0.8%.

[0110] Furthermore, the molded article according to one embodiment of the present invention not only satisfies the above-mentioned thermal stability, but also satisfies excellent tensile strength and elongation, which are measured by the following evaluation methods.

[0111] The molded product according to one embodiment of the present invention has a tensile strength of 100 to 300 kg / cm according to ASTM D638. 2 The elongation rate can be 300 to 600%. Specifically, the tensile strength can be 120 to 250 kg / cm 2 The elongation is 350 to 580%, more specifically, the tensile strength is 150 to 200 kg / cm 2 and the elongation may be 400 to 560%, where the tensile strength and elongation may be measured at room temperature.

[0112] Furthermore, the molded product according to one embodiment of the present invention has excellent aging resistance. Specifically, the molded product according to the present invention also achieves improved effects in heat aging resistance tests. In contrast, the molded product exhibits little change in tensile strength and elongation before and after heating, as measured in accordance with the ASTM D638 test method. The molded product also exhibits excellent hardness. Furthermore, there is almost no change in heat loss and migration resistance, which are the advantages aimed at by the present invention, even in heat aging resistance tests.

[0113] Therefore, the molded product according to one embodiment of the present invention can be used as flooring, wallpaper, tarpaulin, artificial leather, toys, or coating materials for the underside of automobiles, and has good physical properties such as migration and volatility of the plasticizer compared to environmentally friendly plasticizer compositions using DEHCH, which is currently the most commonly used.

[0114] The present invention will be described in more detail below with reference to the following examples. However, the following examples are merely a reference for describing the present invention in detail, and the present invention is not limited thereto, and can be realized in various forms. In addition, unless otherwise defined, all technical and scientific terms have the same meaning as commonly understood by one of ordinary skill in the art to which the present invention belongs. In addition, the terms used in the description of the present invention are merely for the purpose of effectively describing a specific embodiment, and are not intended to limit the present invention.

[0115] In the present invention, unless otherwise specified, all temperatures are expressed in degrees Celsius, and room temperature means 25°C.

[0116] (Evaluation method) 1) Migration resistance: After each test piece was cut into a circle with a diameter of 3 cm, the initial weight (Wi) and the weight of the oil paper before oil absorption (Wq1) were measured to four decimal places. The test piece was placed between the 3M oil paper (55 mm x 85 mm) whose initial weight was measured, and then left in an oven at 70 ° C. for 4 days with a load of 5 kg applied, and then the test piece was taken out and the weight of the test piece and the weight of the oil paper after oil absorption (Wq2) were measured to confirm migration resistance. Migration was calculated by (Wq2-Wq1) / Wi x 100. Here, the migration refers to the amount (%) of plasticizer that flowed out.

[0117] 2)Heating loss: The initial weight (Wi) of each test piece was measured to four decimal places. The test piece was clamped in a 120°C oven, and after 72 hours, the test piece was removed and stored in a thermostatic chamber (room temperature, 25°C) for more than 4 hours. The weight (Wo) of the test piece was then measured and the weight loss ratio (%, W 1 The ratio of heat loss was calculated as (Wi-Wo) / Wi×100.

[0118] 3) Hardness (ASTM D2240): For each test piece, a hardness tester (ASKER CL-150, Shore A) was used in accordance with ASTM D2240, and the needle of the hardness tester ("A" type) was lowered completely, and the hardness value at room temperature was read 10 seconds later. The hardness was calculated by testing five points on each test piece and then calculating the average value.

[0119] 4) Tensile strength, elongation [ASTM D638]: Each test piece was pulled at a cross head speed of 200 mm / min using a UTM test device, and the tensile strength and elongation at the point where the test piece broke were measured. Tensile strength (kgf / cm 2 The calculation of load (kgf) / thickness (cm)×width (cm) was performed, and the elongation (%) was calculated by elongation / initial length×100. The measurements were performed before heating (room temperature) and after heating (120° C., 100 hr).

[0120] The rate of change in tensile strength was calculated as (tensile strength after heating - tensile strength before heating) / tensile strength before heating x 100. The rate of change in elongation was calculated as (elongation after heating - elongation before heating) / elongation before heating x 100.

[0121] Example 1 A 2 L reactor equipped with a temperature sensor, mechanical stirrer, condenser, decanter, and nitrogen injector was charged with diethylhexylcyclohexane ( Bis(2-ethylhexyl) cyclohexane-1,4-dicarboxylate1,400 g of DEHCH and 146.2 g of diethylene glycol (DEG) were added. After addition, the mixture was stirred under nitrogen and heated to 230°C. After heating, 0.5 g of TNBT (Tetra N-butyl Titanate) was added, and a trans-esterification reaction was carried out under the same conditions (reaction time: 8 hours). After the reaction was completed, the mixture was cooled to 90°C, and an alkaline solution (1M NaOH solution) was added, followed by filtering using diatomaceous earth. Then, unreacted alcohol, water, and impurities were removed using a rotary evaporator to obtain the final product, a plasticizer composition.

[0122] The obtained plasticizer composition was analyzed by GPC to confirm the content (wt%) of ester compounds in the composition, such as the content (wt%) of DEHCH relative to the total weight, and the results are shown in Table 1 below.

[0123] Also, a test piece was prepared using the ester-based plasticizer composition produced by the above-mentioned production method. The test piece was prepared by blending 400 g of PVC (polymerization degree 1000) with 200 g of plasticizer, 32 g of composite heat stabilizer (RUP-110), and 80 g of calcium carbonate, and working on a roll mill at 170°C for 3 minutes to produce a 1 mm sheet. After that, the press work was performed at 180°C for 3 minutes of preheating, 10 minutes of heating, and 3 minutes of cooling, and then a test piece with a thickness of 3 mm was prepared.

[0124] The physical properties of the test pieces were measured by the above-mentioned evaluation methods and are shown in Tables 1 and 2 below.

[0125] Example 2 The same manufacturing method as in Example 1 was carried out, but the amount of diethylene glycol was increased to 182.8 g to obtain the final product, an ester plasticizer composition.

[0126] The content (wt%) of ester compounds in the obtained ester plasticizer composition, such as the content (wt%) of DEHCH relative to the total weight, was confirmed by GPC analysis. The results are shown in Table 1 below. In addition, test pieces were prepared in the same manner as in Example 1, and the physical properties measured by the evaluation methods are shown in Tables 1 and 2 below.

[0127] Comparative Example 1 Commercial cyclohexane diester (DEHCH, Hanwha Chemical) was used.

[0128] Test pieces were prepared in the same manner as in Example 1, and the physical properties measured by the evaluation methods described above are shown in Tables 1 and 2 below.

[0129] [Table 1]

[0130] [Table 2]

[0131] As shown in Table 1, when the ester-based plasticizer composition according to the present invention is used, it is found that it has excellent effects on migration resistance and heat loss. Specifically, it was confirmed that all examples according to the present invention satisfied migration resistance of 0.08% or less and heat loss of 0.80% or less. In addition, it was confirmed that all examples according to the present invention showed hardness equal to or greater than that of cyclohexane diester (DEHCH, Comparative Example 1), which is a commercial plasticizer.

[0132] As shown in Table 2, when the ester-based plasticizer composition according to the present invention is used, it is possible to realize tensile strength and elongation equal to or higher than those of the commercially available plasticizer cyclohexane diester (DEHCH, Comparative Example 1), and it also provides a synergistic effect in terms of the rate of change in tensile strength and the rate of change in elongation. In addition, the rate of change was low in the heat aging test.

[0133] From these results, it goes without saying that the ester-based plasticizer composition satisfying the relationship according to the present invention can exhibit excellent effects on migration resistance and heat loss, and it was confirmed that in this effect, a synergistic effect is exhibited as the DEHCH content is reduced. Furthermore, when the reaction conditions (temperature, pressure, time, etc.) are rigorously controlled in order to reduce the DEHCH content, rather than reducing the DEHCH content in the composition, the ester-based plasticizer is polymerized, which makes it impossible to satisfy the relationship according to the present invention and therefore impossible to exhibit the synergistic effect.

[0134] The present invention has been described above with reference to specific and limited examples and comparative examples. However, these are provided to facilitate a more general understanding of the present invention, and the present invention is not limited to the above examples. Various modifications and variations are possible from such descriptions by a person having ordinary knowledge in the field to which the present invention pertains.

[0135] Therefore, the concept of the present invention should not be limited to the above-described embodiments, and all modifications equivalent to or equivalent to the scope of the present claims, as well as the scope of the claims described below, fall within the scope of the concept of the present invention.

Claims

1. An ester-based plasticizer composition represented by the following chemical formula 1, which satisfies the following relational formula 1: 【Chemistry 1】 In the above Chemical Formula 1, n is an integer from 0 to 10, R １ and R ２ are each independently ４－１５ is alkyl, L １ and L ２ are each independently ethylene or propylene. [Relationship 1] 0.05≦|(A ０ -A １～３ ) / A ｎ |≦0.45 In the above Relational Formula 1, A ｎ is 100% by weight of the total weight of the ester plasticizer composition, A ０ is the weight percent of the compound of formula 1 where n=0; A １～３ is the weight percent of the mixture of Formula 1 where n=1 to 3.

2. The ester-based plasticizer composition according to claim 1 , which satisfies the following relational expression 2: [Relationship 2] 0≦A ４～１０ / A １～３ ≦0.2 In the above Relational Formula 2, Relative to the total weight of the ester plasticizer composition, A １～３ is the weight percent of the mixture of Formula 1, where n=1 to 3; A ４～１０ is the weight percent of the mixture of Formula 1 where n=4 to 10.

3. A based on the total weight of the ester-based plasticizer composition ０ The ester-based plasticizer composition of claim 1, wherein the amount of the ester-based plasticizer composition is in the range of 30 to 80% by weight.

4. The R １ and R ２ are each independently ７－１３ 2. The ester plasticizer composition of claim 1, which is a branched alkyl.

5. The R １ and R ２ are each independently ４－６ 2. The ester-based plasticizer composition of claim 1, which is a linear alkyl chain.

6. A polyvinyl chloride resin composition comprising the ester plasticizer composition according to any one of claims 1 to 5.

7. The polyvinyl chloride resin composition according to claim 6, comprising 5 to 100 parts by weight of the ester-based plasticizer composition per 100 parts by weight of the polyvinyl chloride resin.

8. 7. The polyvinyl chloride resin composition of claim 6, further comprising a heat stabilizer, a filler, or a combination thereof.

9. A molded article produced from the polyvinyl chloride resin composition according to claim 6.

10. The molded article according to claim 9, which is a wire covering material, a flooring material, an automobile interior material, a film, a sheet, wallpaper, or a tube.

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