This application claims the benefit of priority based on Korean Patent Application No. 10-2018-0162237 dated December 14, 2018, and all contents disclosed in the literature of the Korean patent application are incorporated as a part of this specification.
[3]
[4]
technical field
[5]
The present invention relates to a plasticizer composition and a resin composition comprising the same, and to a plasticizer composition having excellent safety and basic physical properties while being environmentally friendly, and a resin composition including the same.
[6]
background
[7]
In the polyvinyl chloride compound industry, where high heat resistance and low heat loss are the main required properties, a plasticizer should be used appropriately depending on the purpose. For example, in the case of polyvinyl chloride compounds for use in wires and cables, plasticizers, fillers, stabilizers, At least one selected from the group consisting of a lubricant and a flame retardant may be blended as an additive.
[8]
Currently, diisodecyl phthalate, a plasticizer that is typically used in the wire compound and automobile fabric industries, is an environmental hormone observation substance, so its use is being regulated. Accordingly, there is a demand for the development of an environmentally friendly plasticizer that can replace diisodecyl phthalate.
[9]
However, while having physical properties equal to or superior to that of diisodecyl phthalate, development of an environmentally friendly plasticizer is currently insufficient.
[10]
[11]
[Prior art literature]
[12]
[Patent Literature]
[13]
(Patent Document 1) KR10-0957134B
[14]
DETAILED DESCRIPTION OF THE INVENTION
technical challenge
[15]
An object of the present invention is to improve the physical properties such as plasticizing efficiency, heat loss, heat resistance elongation residual rate, etc., as an environmentally friendly and excellent safety plasticizer composition, and to be equal to or higher than that of existing products with respect to physical properties such as tensile strength, elongation, and transferability To provide a plasticizer composition with improved oil resistance while maintaining it.
[16]
means of solving the problem
[17]
In order to solve the above problems, the present invention provides a cyclohexane-1,2-diester-based material represented by the following formula (1); and diisononyl terephthalate; wherein the cyclohexane-1,2-diester-based material and diisononyl terephthalate provide a weight ratio of 95:5 to 5:95 in a plasticizer composition comprising:
[18]
[Formula 1]
[19]

[20]
In Formula 1, R 1 and R 2 are each independently an alkyl group having 9 or 10 carbon atoms.
[21]
[22]
In addition, the present invention provides a resin composition comprising 100 parts by weight of the resin and 5 to 150 parts by weight of the plasticizer composition.
[23]
Effects of the Invention
[24]
The plasticizer composition of the present invention is environmentally friendly, and has excellent safety and basic physical properties. Accordingly, when the plasticizer composition of the present invention is included in the resin composition, physical properties such as tensile strength, elongation, and transferability are equivalent to or higher than those of existing phthalate products. and can remarkably improve plasticization efficiency, heat loss, heat-resistance elongation residual rate and oil resistance.
[25]
Modes for carrying out the invention
[26]
Hereinafter, the present invention will be described in more detail to help the understanding of the present invention.
[27]
[28]
Definition of Terms
[29]
The term "composition" as used herein includes reaction products and decomposition products formed from the materials of the composition, as well as mixtures of materials comprising the composition.
[30]
As used herein, the prefix "iso-" refers to an alkyl group in which a methyl group or an ethyl group is branched to the main chain of the alkyl group, and in the present specification, unless there is an alkyl group otherwise referred to herein, it is bound to a terminal. Including, it can be used as a generic term for an alkyl group in which a methyl group or an ethyl group is bonded to the main chain as a branched chain.
[31]
As used herein, the term "isononyl group" may mean an alkyl group having a total of 9 carbon atoms in which at least one branch is substituted with one or two methyl groups, one ethyl group, and one propyl group in the main chain, For example, 2-methyloctyl group, 3-methyloctyl group, 4-methyloctyl group, 5-methyloctyl group, 6-methyloctyl group, 3-ethylheptyl group, 2-ethylheptyl group, 2,5-dimethylheptyl group tyl group, 2,3-dimethylheptyl group, 4,5-dimethylheptyl group, 3-ethyl-4-methylhexyl group, 2-ethyl-4-methylhexyl group, or 2-propylhexyl group As a term used, commercially used isononyl alcohol (CAS No.: 68526-84-1, 27458-94-2) may refer to a composition of isomers having a branching degree of 1.2 to 1.9, and In some cases, n-nonyl groups may also be included.
[32]
The term "straight vinyl chloride polymer" as used herein, as one of the types of vinyl chloride polymer, may mean polymerized through suspension polymerization or bulk polymerization, and has a size of several tens to several hundreds of micrometers. It refers to a polymer having a form of porous particles with a large amount of pores distributed, no cohesiveness, and excellent flowability.
[33]
The term "paste vinyl chloride polymer" as used herein, as one of the types of vinyl chloride polymer, may mean polymerized through microsuspension polymerization, microseed polymerization, or emulsion polymerization, It refers to a polymer having a size of several thousand nanometers and has poor flowability as fine, dense, void-free particles.
[34]
The terms 'comprising', 'having' and their derivatives are not intended to exclude the presence of any additional component, step or procedure, whether or not they are specifically disclosed. For the avoidance of any doubt, all compositions claimed through use of the term 'comprising', unless stated to the contrary, contain any additional additives, adjuvants, or compounds, whether polymeric or otherwise. may include In contrast, the term 'consisting essentially of' excludes from the scope of any subsequent description any other component, step or procedure, except as not essential to operability. The term 'consisting of' excludes any component, step or procedure not specifically described or listed.
[35]
[36]
How to measure
[37]
In the present specification, analysis of the content of components in the composition is performed through gas chromatography measurement, and Agilent's gas chromatography instrument (product name: Agilent 7890 GC, column: HP-5, carrier gas: helium (flow rate 2.4 mL/min)) , detector: FID, injection volume: 1uL, initial value: 70℃/4.2min, end value: 280℃/7.8min, program rate: 15℃/min).
[38]
In the present specification, 'hardness' means the shore hardness (Shore "A" and / or Shore "D") at 25 ° C using ASTM D2240, measured under the conditions of 3T 10s, and plasticized It can be an index to evaluate the efficiency, and the lower it is, the better the plasticization efficiency is.
[39]
In the present specification, 'tensile strength' is a test device, UTM (manufacturer; Instron, model name; 4466), according to the ASTM D638 method, and the cross head speed is 200 mm/min (1T) ), measure the point at which the specimen is cut, and calculate by Equation 1 below.
[40]
[Equation 1]
[41]
Tensile strength (kgf/cm 2 ) = load value (kgf) / thickness (cm) x width (cm)
[42]
In the present specification, the 'elongation rate' refers to the point at which the specimen is cut after pulling the cross head speed to 200 mm/min (1T) using the UTM according to the ASTM D638 method. Then, it is calculated by Equation 2 below.
[43]
[Equation 2]
[44]
Elongation (%) = length after stretching / initial length x 100
[45]
In the present specification, 'migration loss' refers to obtaining a test piece having a thickness of 2 mm or more according to KSM-3156, attaching a plate to both sides of the test piece, and applying a load of 1 kgf/cm 2 . After leaving the test piece in a hot air circulation oven (80°C) for 72 hours, take it out and cool it at room temperature for 4 hours. Then, after removing the plates attached to both sides of the test piece, measure the weight before and after leaving the plates in the oven to calculate the transfer loss by Equation 3 below. Here, the material of the plate may be various such as PS (Polystyrene), ABS, Glass, and the specimen itself (Specimen plate), and the plate material used for measurement in this specification is PS.
[46]
[Equation 3]
[47]
Transition loss (%) = {(Initial weight of test piece at room temperature - Weight of test piece after leaving the oven) / Initial weight of test piece at room temperature} x 100
[48]
In the present specification, 'volatile loss' refers to measuring the weight of the specimen after working the specimen at 80°C for 72 hours.
[49]
[Equation 4]
[50]
Loss on heating (wt%) = {(initial specimen weight - specimen weight after work) / initial specimen weight} x 100
[51]
In the case of the various measurement conditions, detailed conditions such as temperature, rotation speed, time, etc. may be slightly different depending on the case, and in the case of different conditions, the measurement method and conditions are separately specified.
[52]
[53]
Hereinafter, the present invention will be described in more detail to help the understanding of the present invention.
[54]
The terms or words used in the present specification and claims are not to be construed as being limited to their ordinary or dictionary meanings, and the inventor may properly define the concept of the term in order to best describe his invention. Based on the principle that there is, it should be interpreted as meaning and concept consistent with the technical idea of ​​the present invention.
[55]
[56]
The plasticizer composition according to an embodiment of the present invention includes a cyclohexane-1,2-diester-based material represented by the following Chemical Formula 1; and a diisononyl terephthalate-based material.
[57]
[Formula 1]
[58]

[59]
In Formula 1, R 1 and R 2 are each independently an alkyl group having 9 or 10 carbon atoms.
[60]
In addition, the plasticizer composition according to an embodiment of the present invention may further include an additional plasticizer, and the additional plasticizer may be an epoxidized oil or a trimellitate-based material, and at least one material selected from these may be applied as an additional plasticizer. can
[61]
[62]
According to an embodiment of the present invention, the cyclohexane-1,2-diester-based material is represented by Chemical Formula 1, and may give the plasticizer composition an environment-friendly property of excluding a phthalate component. In addition, properties such as plasticizing efficiency and elongation of the plasticizer composition may be further improved.
[63]
At this time, when the bonding position of the diester group in cyclohexane is not the 1st and 2nd carbons, there may occur a problem in that compression transferability and stress transferability are poor.
[64]
In the cyclohexane-1,2-diester-based material, two alkyl groups R 1 and R 2 bonded to the diester group are each independently an alkyl group having 9 or 10 carbon atoms, and when an alkyl group having less than 9 carbon atoms is bonded, heating There is a fear that the mechanical properties such as weight loss, migration loss and tensile strength deteriorate and affect the workability, and when an alkyl group having more than 10 carbon atoms is bonded, workability and plasticizing efficiency may be adversely affected. In order to optimize this effect, an alkyl group having 9 or 10 carbon atoms may be preferably selected.
[65]
For example, R 1 and R 2 are the same as or different from each other, and each independently is one selected from the group consisting of n-nonyl group, isononyl group, 2-propylheptyl group, isodecyl group and n-decyl group. and among them, as one selected from the group consisting of an isononyl group, a 2-propylheptyl group and an isodecyl group, it is preferable that a branched alkyl group is applied.
[66]
When the cyclohexane-1,2-diester-based material represented by Formula 1 is directly prepared, cyclohexane 1,2-dicarboxylic acid or a derivative thereof and an alcohol may be prepared by direct esterification or transesterification reaction. have.
[67]
The cyclohexane 1,2-dicarboxylic acid derivative may be at least one selected from the group consisting of an anhydride of cyclohexane-1,2-dicarboxylic acid and/or an alkyl ester of cyclohexane 1,2-dicarboxylic acid. In this case, the alkyl ester may be an alkyl ester having 1 to 12 carbon atoms.
[68]
The alkyl group of the finally prepared cyclohexane-1,2-diester has 9 or 10 carbon atoms, and it is preferable that the same alkyl group as described above is applied, and these alkyl groups may be derived from the alcohol used in the preparation.
[69]
[70]
When the cyclohexane-1,2-diester-based material represented by Formula 1 is prepared by the direct esterification reaction, the alcohol is 2 to 10 moles, 2 to 8 moles, 2 to 6 moles, or 2 to 5 moles may be used, and 2 to 5 moles of these may be used.
[71]
The direct esterification reaction may be performed in the presence of a catalyst, and the catalyst may be at least one selected from the group consisting of inorganic acids, organic acids, and Lewis acids, and among them, at least one selected from the group consisting of organic acids and Lewis acids. can
[72]
The inorganic acid may be at least one selected from the group consisting of sulfuric acid, hydrochloric acid and phosphoric acid.
[73]
The organic acid may be at least one selected from the group consisting of p-toluenesulfonic acid, methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid and alkyl sulfuric acid.
[74]
The Lewis acid is an aluminum derivative (aluminum oxide, aluminum hydroxide), a tin derivative (C 3 to C 12 fatty acid tin, tin oxide, tin hydroxide), a titanium derivative (C 3 to C 8 tetraalkyl titanate, titanium oxide, hydroxide Titanium), lead derivatives (lead oxide, lead hydroxide), and zinc derivatives (zinc oxide, zinc hydroxide) may be at least one selected from the group consisting of.
[75]
[76]
When the catalyst is a homogeneous catalyst, 0.01 to 5 parts by weight or 0.01 to 3 parts by weight based on 100 parts by weight of the total of the cyclohexane 1,2-dicarboxylic acid or its derivative and alcohol, 0.01 to 3 parts by weight of which It is preferably used in parts by weight.
[77]
When the catalyst is a heterogeneous catalyst, 0.5 to 200 parts by weight or 0.5 to 100 parts by weight based on 100 parts by weight of the total of cyclohexane 1,2-dicarboxylic acid or a derivative thereof and alcohol, 0.5 to 200 parts by weight of which It is preferable to use it as a part.
[78]
The direct esterification reaction may be carried out at 100 to 280 °C, 130 to 250 °C, or 150 to 230 °C, of ​​which it is preferably carried out at 150 to 230 °C.
[79]
The direct esterification reaction may be performed for 3 to 30 hours or 3 to 25 hours, of which 3 to 25 hours is preferable.
[80]
[81]
Meanwhile, when the cyclohexane-1,2-diester-based material is prepared by the transesterification reaction, it may be prepared by the transesterification reaction of the cyclohexane 1,2-dicarboxylic acid derivative and alcohol.
[82]
The derivative of cyclohexane 1,2-dicarboxylic acid may be an alkyl ester of cyclohexane 1,2-dicarboxylic acid, and preferably, a methyl ester of cyclohexane 1,2-dicarboxylic acid to facilitate separation of the reaction product. can be used
[83]
Based on 1 mole of the cyclohexane 1,2-dicarboxylic acid derivative, 2 to 10 moles, 2 to 8 moles, 2 to 6 moles, or 2 to 5 moles of the alcohol may be used, of which 2 to 5 moles are used. It is preferable to be
[84]
The transesterification reaction may be performed in the presence of a catalyst, and in this case, the reaction time may be shortened.
[85]
The catalyst may be at least one selected from the group consisting of a Lewis acid and an alkali metal.
[86]
The Lewis acid is as described in the description of the direct esterification reaction, aluminum derivatives (aluminum oxide, aluminum hydroxide), tin derivatives (C 3 to C 12 fatty acid tin, tin oxide, tin hydroxide), titanium derivatives (C 3 to C 8 may be at least one selected from the group consisting of tetraalkyl titanate, titanium oxide, titanium hydroxide), lead derivatives (lead oxide, lead hydroxide), and zinc derivatives (zinc oxide, zinc hydroxide).
[87]
In addition, the alkali metal may be at least one selected from the group consisting of sodium alkoxide, potassium alkoxide, sodium hydroxide and potassium hydroxide, and a single or mixed catalyst of two or more of the metal catalyst may be used.
[88]
The catalyst may be used in an amount of 0.01 to 5 parts by weight or 0.01 to 3 parts by weight based on 100 parts by weight of the sum of the cyclohexane 1,2-dicarboxylic acid derivative and the alcohol, of which 0.01 to 3 parts by weight is used desirable.
[89]
The transesterification reaction may be carried out at 120 to 250 °C, 135 to 230 °C, or 140 to 220 °C, of ​​which it is preferably carried out at 140 to 220 °C.
[90]
The transesterification reaction may be performed for 0.5 to 10 hours or 0.5 to 8 hours, of which 0.5 to 8 hours is preferable.
[91]
[92]
In the direct esterification reaction or transesterification reaction, at least one selected from the group consisting of benzene, toluene, xylene and cyclohexane is added to promote the outflow of lower alcohols such as water or methanol produced by the reaction. It can be added, and commercially available nitrogen, etc. can be used as entrainment for the same purpose.
[93]
The cyclohexane-1,2-diester-based material represented by Formula 1 prepared by the direct esterification reaction or the transesterification reaction may be purified by performing a separate post-treatment. The post-treatment may be at least one selected from the group consisting of catalyst inactivation treatment (neutralization treatment, base treatment), water washing treatment, distillation (reduced pressure or dehydration treatment), and adsorption purification treatment.
[94]
[95]
Unlike the above manufacturing method, a manufacturing method including a step of converting a dialkyl phthalate-based material into a cyclohexane-1,2-diester-based material by a hydrogenation reaction in the presence of a metal catalyst may be applied.
[96]
The hydrogenation step is a reaction for removing the aromaticity of the benzene ring of phthalate by adding hydrogen in the presence of a metal catalyst, and may be a kind of reduction reaction.
[97]
The hydrogenation reaction synthesizes a cyclohexane-1,2-diester-based material by reacting the phthalate-based material with hydrogen under a metal catalyst, and the reaction condition is a benzene ring without affecting the carbonyl group substituted in benzene. It may include all conventional reaction conditions capable of hydrogenating only .
[98]
The hydrogenation reaction may be carried out further including an organic solvent such as ethanol, but is not limited thereto. As the metal catalyst, a Rh/C catalyst, a Pt catalyst, a Pd catalyst, etc., which are generally used for hydrogenating the benzene ring, may be used, but is not limited thereto as long as the hydrogenation reaction as described above is possible.
[99]
[100]
According to an embodiment of the present invention, the plasticizer composition includes diisononyl terephthalate together with the cyclohexane-1,2-diester-based material.
[101]
The diisononyl terephthalate is an existing product among terephthalate-based plasticizers that can replace diisononyl phthalate. It has excellent mechanical properties such as tensile strength and elongation, but has extremely poor plasticization efficiency, oil resistance and heat-resistance elongation residual. And the tensile residual ratio is poor, there is a difficulty in being used as an alternative product.
[102]
However, as in the present invention, when mixed with the cyclohexane-1,2-diester-based material, the excellent physical properties of diisononyl terephthalate are maintained close to the same level, and the poor physical properties can be improved synergistic effect. have.
[103]
The weight ratio of the cyclohexane-1,2-diester-based material and the diisononyl terephthalate-based material is the upper limit of 99:1, 95:5, 90:10, 85:15, 80:20, 75:25, 70 :30, or 60:40, with lower bounds of 1:99, 5:95, 10:90, 15:85, 20:80, 25:75, 30:70, 40:60 or 50:50 days can Preferred ranges among these may be 95:5 to 5:95, 90:10 to 10:90, more preferably 80:20 to 20:80, and even more preferably 70:30 to 30: 70, and may be 50:50 to 30:70. In order to achieve the above synergistic effect, it is desirable to satisfy such a ratio range, and significant improvement in the effect of heat loss and oil resistance and thermal elongation residual rate improvement can be expected, and mechanical properties of tensile strength and elongation can also be expected. have.
[104]
In particular, the plasticizer composition has excellent tensile strength and elongation, and excellent transferability, so that it cannot be applied to the calendaring industry that manufactures sheets, etc., but properties such as elongation residual rate, tensile residual rate, and oil resistance will be significantly improved. Considering that it can be, it may be more suitable for the compound industry that manufactures wires and the like.
[105]
According to an embodiment of the present invention, an additional plasticizer may be further included, and the additional plasticizer may be selected from an epoxidized oil and a trimellitate-based material. This additive plasticizer can complement the transferability and heat loss in mixing the cyclohexane-1,2-diester-based material and diisononyl terephthalate, and ensure stable improvement in tensile strength and elongation. have.
[106]
The additive plasticizer is a weight ratio of the total weight of the cyclohexane-1,2-diester-based material and diisononyl terephthalate, and the weight ratio of the total weight of the two materials to the weight of the additive plasticizer is 99:1, 95 as an upper limit. :5, 90:10, 85:15, 80:20, 75:25, 70:30, or 60:40 with lower bounds of 1:99, 5:95, 10:90, 15:85, 20:80, 25:75, 30:70, 40:60 or 50:50. Among these, a preferred range may be 90:10 to 10:90, or 90:10 to 30:70, and more preferably 80:20 to 50:50.
[107]
When an additional plasticizer is used together in such a range, the quality stability of the plasticizer product can be further improved, and the mixing ratio of the cyclohexane-1,2-diester-based material and diisononyl terephthalate can be applied more flexibly. Advantages can be expected.
[108]
According to an embodiment of the present invention, the epoxidized oil may further improve thermal stability, loss on heating, oil resistance and absorption rate of the plasticizer composition. In addition, the epoxy oil can improve mechanical properties such as tensile strength and elongation of the plasticizer composition, and further improvement of heat resistance can be expected.
[109]
The epoxidized oil is epoxidized soybean oil, epoxidized castor oil, epoxidized linseed oil, epoxidized palm oil, epoxidized stearate ), epoxidized oleate, epoxidized tall oil, and epoxidized linoleate may be at least one selected from the group consisting of, among these, epoxidized soybean oil and epoxidized linoleate oil. At least one selected from the group consisting of is preferable.
[110]
The epoxidized oil may be prepared directly or a commercially available material may be used.
[111]
[112]
The trimellitate-based material may impart environmental-friendly properties and excellent safety to the plasticizer composition. In addition, properties such as migration resistance, heat loss, tensile residual ratio, elongation residual ratio, and oil resistance of the plasticizer composition may be further improved.
[113]
In particular, the trimellitate-based material may be selected from the group consisting of tri(2-ethylhexyl) trimellitate, triisononyl trimellitate and tri(2-propylheptyl) trimellitate, preferably tri (2-ethylhexyl) trimellitate, or triisononyl trimellitate.
[114]
When the above material is selected as the trimellitate-based material, it can contribute to securing the plasticizing efficiency, migration resistance, heating loss, tensile residual ratio, elongation residual ratio, and oil resistance equivalent to or higher than that of diisodecyl phthalate.
[115]
When the trimellitate-based material is directly prepared, it may be prepared by direct esterification or transesterification reaction between trimellitic acid or a derivative thereof and alcohol.
[116]
The derivative of trimellitic acid may be at least one selected from the group consisting of an anhydride of trimellitic acid and an alkyl ester of trimellitic acid, wherein the alkyl ester may be an alkyl ester having 1 to 12 carbon atoms.
[117]
The finally prepared alkyl group of trimellitate has 8 to 10 carbon atoms, and preferably has 8 to 9 carbon atoms.
[118]
When the trimellitate-based material represented by Chemical Formula 2 is prepared by the direct esterification reaction, the alcohol content is 3 to 15 moles, 3 to 12 moles, 3 to 10 moles based on 1 mole of the trimellitic acid or its derivative. It may be used in moles, 3 to 8 moles, or 3 to 6 moles, and it is preferable to use 3 to 6 moles of them.
[119]
In addition, the description of the direct esterification reaction is the same as described in the method for preparing the cyclohexane-1,2-diester-based material.
[120]
Meanwhile, when the trimellitate-based material represented by Formula 2 is prepared by the transesterification reaction, it may be prepared by the transesterification reaction of the trimellitic acid derivative and alcohol. Here, the derivative of trimellitic acid may be an alkyl ester of trimellitic acid.
[121]
Based on 1 mol of the trimellitic acid derivative, 3 to 15 mol, 3 to 12 mol, or 3 to 10 mol of the alcohol may be used, and 3 to 10 mol of the alcohol is preferably used.
[122]
In addition, the description of the transesterification reaction is the same as described in the method for preparing the cyclohexane-1,2-diester-based material.
[123]
[124]
The resin composition according to another embodiment of the present invention includes 100 parts by weight of the resin, and 5 to 150 parts by weight of the above-described plasticizer composition. The plasticizer composition may be included 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.
[125]
As the resin, a resin known in the art may be used. For example, at least one selected from the group consisting of straight vinyl chloride polymer, paste vinyl chloride polymer, ethylene vinyl acetate copolymer, ethylene polymer, propylene polymer, polyketone, polystyrene, polyurethane, natural rubber, synthetic rubber, and thermoplastic elastomer Mixtures and the like may be used, but the present invention is not limited thereto.
[126]
In general, the resin in which the plasticizer composition is used may be manufactured into a resin product through melt processing or plastisol processing, and the melt processing resin and the plastisol processing resin may be produced differently according to each polymerization method.
[127]
For example, when a vinyl chloride polymer is used for melt processing, solid resin particles with a large average particle diameter are used because it is prepared by suspension polymerization, etc., and this vinyl chloride polymer is called a straight vinyl chloride polymer, and is used for plastisol processing. In this case, a resin in a sol state is used as fine resin particles prepared by emulsion polymerization, etc., and such a vinyl chloride polymer is called a paste vinyl chloride resin.
[128]
At this time, in the case of the straight vinyl chloride polymer, the plasticizer is preferably included in the range of 5 to 80 parts by weight based on 100 parts by weight of the polymer, and in the case of the paste vinyl chloride polymer, in the range of 40 to 120 parts by weight based on 100 parts by weight of the polymer. It is preferable to include in
[129]
The resin composition may further include a filler. The filler may 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.
[130]
The plasticizer composition according to an embodiment of the present invention may be preferably applied to a straight vinyl chloride polymer, and thus may be melt-processed, and as a processing method to be described later, a resin product applied to processing such as calendering, extrusion, injection, etc. It can be used as a plasticizer.
[131]
As the filler, any filler known in the art may be used, and the filler is not particularly limited. For example, it may be a mixture of one or more selected from silica, magnesium carbonate, calcium carbonate, coal, talc, magnesium hydroxide, titanium dioxide, magnesium oxide, calcium hydroxide, aluminum hydroxide, aluminum silicate, magnesium silicate and barium sulfate.
[132]
In addition, the resin composition may further include other additives such as a stabilizer, if necessary. Other additives such as the stabilizer may be, for example, 0 to 20 parts by weight, preferably 1 to 15 parts by weight, based on 100 parts by weight of the resin.
[133]
The stabilizer may include, for example, a calcium-zinc (Ca-Zn-based) stabilizer such as a calcium-zinc complex stearate, but is not particularly limited thereto.
[134]
The resin composition may be applied to both melt processing and plastisol processing as described above, for example, melt processing may be calendering processing, extrusion processing, or injection processing, and plastisol processing may be coating processing, etc. This can be applied.
[135]
The resin composition may be used in the manufacture of electric wires, flooring materials, automobile interior materials, films, sheets or tubes.
[136]
[137]
Hereinafter, embodiments of the present invention will be described in detail so that those of ordinary skill in the art can easily carry out the present invention. However, the present invention may be embodied in various different forms and is not limited to the embodiments described herein.
[138]
[139]
Preparation Example 1: diisononyl cyclohexane-1,2-diester (1,2-DINCH)
[140]
462.5 g of anhydrous cyclohexane-1,2-dicarboxylic acid, 1,296 g of isononyl alcohol, 1.55 g of tetraisopropyl titanate as catalyst was added, the reaction temperature was set to 230 °C, and nitrogen gas was continuously added, the esterification reaction was performed directly for about 6 hours, and the reaction was completed when the acid value reached 0.1.
[141]
After completion of the reaction, in order to remove unreacted raw materials, distillation extraction was performed under reduced pressure. After distillation extraction, 1,240 g (yield: 97%) of diisononyl cyclohexane-1,2-diester was prepared through a neutralization process, a dehydration process, and a filtration process.
[142]
[143]
Preparation Example 2: diisononyl terephthalate (DINTP)
[144]
Purified Terephthalic Acid (PTA) 498.0 g, isononyl alcohol (INA) 1,296 g (PTA:INA molar ratio (1.0 ): (3.0)), 1.54 g (0.31 parts by weight based on 100 parts by weight of PTA) of a titanium-based catalyst (TIPT, tetra isopropyl titanate) was added as a catalyst, and the temperature was gradually raised to about 170°C. Generation of water was started at about 170°C, and the ester reaction was performed for about 4.5 hours while nitrogen gas was continuously added at a reaction temperature of about 220°C and atmospheric pressure, and the reaction was terminated when the acid value reached 0.01.
[145]
After completion of the reaction, distillation is performed under reduced pressure for 0.5 to 4 hours to remove unreacted raw materials. In order to remove unreacted raw materials below a certain content level, steam extraction is performed under reduced pressure for 0.5 to 3 hours using steam, the reaction solution temperature is cooled to about 90° C., and neutralization treatment is performed using an alkali solution. . In addition, water washing may be performed, and then the reaction solution is dehydrated to remove moisture. A filter medium was added to the water-removed reaction solution, stirred for a certain time, and then filtered to finally obtain 1,243 g of DINTP (yield: 99.0%).
[146]
[147]
Preparation Example 3: Diisononyl cyclohexane-1,4-diester (1,4-DINCH)
[148]
In the same manner as in Preparation Example 1, except that 516.3 g of cyclohexane-1,4-dicarboxylic acid was used instead of the anhydrous cyclohexane-1,2-dicarboxylic acid, diisononyl cyclohexane-1 1,256 g of ,4-diester (yield: 98%) was prepared.
[149]
[150]
Preparation Example 4: Di (2-ethylhexyl) cyclohexane-1,2-diester (1,2-DEHCH)
[151]
In the same manner as in Preparation Example 1, except that 1,170 g of 2-ethylhexanol was used instead of isononyl alcohol of Preparation Example 1, 1,166 g of di(2-ethylhexyl)cyclohexane-1,4-diester (Yield: 98) %) was prepared.
[152]
[153]
Preparation 5: Tri (2-ethylhexyl) trimellitate (TEHTM)
[154]
Tri(2-ethylhexyl) trimellitate (TEHTM) 1,060 g (yield: 97%) in the same manner as in Preparation Example 1, except that 384 g of trimellitic anhydride and 1,170 g of 2-ethylhexyl alcohol were added to the reactor. ) was obtained.
[155]
[156]
Preparation Example 6: Triisononyl trimellitate (TINTM)
[157]
1,140 g (yield: 97%) of triisononyl trimellitate (TINTM) was obtained in the same manner as in Preparation Example 1, except that 384 g of trimellitic anhydride and 1,296 g of isononyl alcohol were added to the reactor.
[158]
[159]
Examples and Comparative Examples
[160]
The plasticizer compositions of Examples and Comparative Examples using the materials prepared in Preparation Examples 1 to 6, epoxidized oil, diisodecyl phthalate (DIDP), di(2-ethylhexyl) terephthalate, and hydrogenated materials of terephthalate prepared, and summarized in Tables 1 and 2 below. The evaluation of the physical properties of the plasticizer composition was performed according to the following experimental items. Commercial products (products of LG Chem (DEHTP and DIDP)) were used for materials other than those prepared in Preparation Example.
[161]
[Table 1]
1,2-DINCH DINTP ESO TEHTM/TINTM
Example 1 70 30 - -
Example 2 30 70 - -
Example 3 50 50 - -
Example 4 40 60 - -
Example 5 60 40 - -
Example 6 20 30 - 50 (TEHTM)
Example 7 30 40 - 30 (TINTM)
Example 8 40 40 20 -
Example 9 90 10 - -
Example 10 10 90 - -
[162]
[Table 2]
cyclohexane terephthalate DIDP
Comparative Example 1 - - 100
Comparative Example 2 1,2-DINCH 100 - -
Comparative Example 3 - DINTP 100 -
Comparative Example 4 1,4-DEHCH 90 DINTP 10 -
Comparative Example 5 1,4-DINCH 70 DEHTP 30 -
Comparative Example 6 1,2-DEHCH 50 DINTP 50 -
Comparative Example 7 1,2-DINCH 50 DEHTP 50 -
[163]
1) The contents of Tables 1 and 2 above are all in weight %.
[164]
2) ESO: epoxidized soybean oil (Sajohaepyo, ESO)
[165]
3) 1,4-DEHCH: di(2-ethylhexyl) cyclohexane 1,4-diester (Hanwha Chemical, Eco-DEHCH)
[166]
[167]
Experimental Example 1: Evaluation of sheet performance
[168]
Using the plasticizers of Examples and Comparative Examples, specimens were manufactured under the following prescription and manufacturing conditions according to ASTM D638.
[169]
(1) Prescription : 100 parts by weight of straight vinyl chloride polymer (LS100, LG Chem), 50 parts by weight of plasticizer, 40 parts by weight of filler (OMYA 1T), 5 parts by weight of stabilizer (RUP-144) and 0.3 parts by weight of lubricant (St-A) parts by weight
[170]
(2) Mixing : Mixing at 700 rpm at 98℃
[171]
(3) Specimen production : 1T, 2T, and 3T sheets were produced by working with a roll mill at 160°C for 4 minutes and pressing at 180°C for 3 minutes (low pressure) and 2.5 minutes (high pressure)
[172]
(4) Evaluation items
[173]
1) Hardness: Using ASTM D2240, the shore hardness (Shore "A" and "D") at 25 ℃ was measured with a 3T specimen for 10 seconds. It is evaluated that the smaller the numerical value, the better the plasticization efficiency.
[174]
2) Tensile strength: After pulling the cross head speed to 200 mm/min using a test device UTM (manufacturer; Instron, model name; 4466) according to ASTM D638 method, 1T specimen The cut point was measured. Tensile strength was calculated as follows:
[175]
Tensile strength (kgf/cm 2 ) = load value (kgf) / thickness (cm) x width (cm)
[176]
3) Elongation rate: According to ASTM D638 method, after pulling the cross head speed to 200 mm/min using the UTM, measuring the point at which the 1T specimen is cut, the elongation is calculated as follows Calculated as:
[177]
Elongation (%) = length after stretching / initial length x 100 was calculated.
[178]
4) Tensile and elongation residual ratio measurement: The tensile and elongation residual ratio measurement is to measure the tensile strength and elongation remaining in the specimen after applying heat at 113°C for 168 hours. The measurement method is the same as the tensile strength and elongation measurement method do.
[179]
5) Measurement of migration loss: A test piece with a thickness of 2 mm or more was obtained according to KSM-3156, and after attaching PS plates to both sides of the 1T specimen, a load of 1 kgf/cm 2 was applied. The specimens were left in a hot air circulation oven (80° C.) for 72 hours, then taken out and cooled at room temperature for 4 hours. Then, the weight of the specimen, from which the PS plate attached to both sides of the specimen was removed, was measured before and after leaving it in the oven, and the transfer loss was calculated by the following formula.
[180]
Transition loss (%) = {(Initial weight of test piece at room temperature - Weight of test piece after leaving the oven) / Initial weight of test piece at room temperature} x 100
[181]
5) volatile loss: After working the prepared specimen at 113° C. for 168 hours, the weight of the specimen was measured.
[182]
Loss on heating (wt%) = initial specimen weight - (113 °C, specimen weight after 168 hours of operation) / initial specimen weight x 100 was calculated.
[183]
6) Stress test (stress resistance): After a specimen having a thickness of 2 mm was left in a bent state at 23° C. for 72 hours, the degree of migration (the degree of seepage) was observed, and the result was written as a numerical value, at 0 The closer it was, the better the properties were.
[184]
7) Cold resistance: After leaving 5 manufactured 2T specimens at a specific temperature for 3 minutes, the temperature was measured when 3 out of 5 were damaged by hitting.
[185]
8) Oil resistance: The oil resistance test, which measures the resistance to transition to oil, is conducted based on ASTM D1239-14. After soaking a 1 mm thick specimen using ASTM standard IRM-902 oil at 70°C for 4 hours, , After leaving at room temperature for more than 12 hours and removing the oil, the tensile and elongation residuals were measured.
[186]
(5) Evaluation results
[187]
The evaluation results of the above items are shown in Tables 3 and 4 below.
[188]
[Table 3]
Hardness Tensile strength (kgf/cm 2 ) Tensile Residual Rate (%) Elongation (%) Kidney Residual Rate (%)
division Shore A Shore D
Example 1 92.3 46.2 179.6 109.4 286.6 88.7
Example 2 93.0 47.1 185.7 105.8 296.7 92.6
Example 3 92.7 46.7 184.6 106.2 291.4 91.4
Example 4 92.8 46.8 185.7 108.4 293.5 91.8
Example 5 92.5 46.5 182.3 103.8 285.9 89.5
Example 6 93.1 48.5 187.8 103.4 291.0 94.3
Example 7 93.9 49.0 188.9 104.9 296.8 88.2
Example 8 92.1 46.8 187.3 105.5 289.1 90.7
Example 9 92.0 46.1 168.7 108.9 288.2 82.3
Example 10 94.0 48.8 189.3 99.5 288.7 92.5
Comparative Example 1 93.8 48.9 168.5 96.1 273.7 83.1
Comparative Example 2 91.9 46.1 178.2 109.3 287.1 59.4
Comparative Example 3 94.1 49.0 191.7 98.6 297.5 92.8
Comparative Example 4 90.2 44.7 156.2 102.0 256.3 42.1
Comparative Example 5 92.1 46.0 168.4 92.4 265.0 58.0
Comparative Example 6 91.3 45.5 170.6 88.4 283.4 78.8
Comparative Example 7 91.1 45.4 172.4 90.2 276.5 80.4
[189]
[Table 4]
division Performance loss (%) Heat loss (%) Cold resistance (℃) oil resistance stress resistance
TSR TER
Example 1 3.44 8.92 -31.5 94.3 78.4 0.5
Example 2 3.91 5.04 -32.0 89.8 80.5 1.0
Example 3 3.52 6.34 -32.5 92.6 80.2 1.0
Example 4 3.50 6.01 -32.0 92.8 80.6 1.0
Example 5 3.43 6.78 -31.5 92.0 79.6 1.0
Example 6 0.78 2.54 -27.0 88.2 80.9 0.5
Example 7 1.31 4.15 -30.0 89.5 86.9 0.5
Example 8 1.66 5.00 -31.0 92.9 83.5 0.5
Example 9 3.40 9.52 -31.5 92.4 76.7 1.0
Example 10 3.32 2.30 -33.0 90.2 81.1 1.0
Comparative Example 1 2.28 5.64 -25.0 88.0 71.1 0.5
Comparative Example 2 4.22 14.6 -31.0 81.5 71.9 2.0
Comparative Example 3 3.30 2.24 -33.0 83.7 75.3 3.0
Comparative Example 4 4.67 17.5 -31.0 82.3 62.1 3.0
Comparative Example 5 6.20 11.2 -32.0 80.1 65.3 3.0
Comparative Example 6 3.34 8.63 -31.0 84.2 73.3 2.0
Comparative Example 7 3.80 8.60 -30.0 82.0 70.2 2.0
[190]
Referring to Tables 3 and 4, in the case of Examples 1 to 10 to which the plasticizer composition according to an embodiment of the present invention is applied, it can be confirmed that the plasticization efficiency is improved compared to Comparative Example 1, which is DIDP used as an existing product, and cold resistance It can also be seen that there has been a significant improvement. In addition, significant improvements in tensile strength, elongation, and oil resistance can be seen, and in particular, it is confirmed that the improvement is clearly made in the case of residual ratio characteristics.
[191]
In addition, Comparative Examples 2 and 3 were not mixed, unlike in Examples, and Comparative Example 2 was confirmed to be extremely poor in heat loss, oil resistance, and tensile residual ratio, and Comparative Example 3 was plasticizing efficiency, oil resistance, It can be seen that the stress resistance is extremely poor, so it can be seen that it is difficult to commercialize it by itself, but if you look at Examples 1 to 5, most of the physical properties are excellent properties that 1,2-DINCH and DINTP have. It can be seen that the evaluation was biased, and in particular, it is confirmed that the effect is increased through synergy compared to the two materials for elongation, oil resistance, and stress resistance. Due to this, it can be confirmed that excellent physical properties can be selectively obtained, and further, there is an unexpected improvement.
[192]
Furthermore, in Comparative Examples 4 and 5 using a material obtained by hydrogenating terephthalate, tensile strength and elongation were inferior to those of Examples, and it was confirmed that the elongation residual rate was very poor, making it impossible to use as a compound industry product.
[193]
In addition, Comparative Example 6 using a cyclohexane 1,2-diester-based material having 8 carbon atoms and Comparative Example 7 using di(2-ethylhexyl)terephthalate instead of diisononyl terephthalate as a terephthalate-based material It can be seen that the tensile residual ratio and the elongation residual ratio are inferior compared to the Examples, and deterioration of physical properties occurred, not improvement, even compared to Comparative Example 1, which is an existing product.
Claims
[Claim 1]
a cyclohexane-1,2-diester-based material represented by the following formula (1); And diisononyl terephthalate; and wherein the cyclohexane-1,2-ester-based materials and diisononyl terephthalate at a weight ratio of 95: The plasticizer composition is 5 to 5: 95: [Chemical Formula 1] wherein In Formula 1, R 1 and R 2 are each independently an alkyl group having 9 or 10 carbon atoms.
[Claim 2]
The plasticizer composition of claim 1, wherein the cyclohexane-1,2-diester-based material and diisononyl terephthalate have a weight ratio of 90:10 to 10:90.
[Claim 3]
The plasticizer composition according to claim 1, wherein the weight ratio of the cyclohexane-1,2-diester-based material and diisononyl terephthalate is 80:20 to 20:80.
[Claim 4]
The plasticizer composition of claim 1, wherein R 1 and R 2 are each independently selected from the group consisting of an n-nonyl group, an isononyl group, a decyl group, an isodecyl group, and a 2-propylheptyl group.
[Claim 5]
The plasticizer composition of claim 1, wherein R 1 and R 2 are each independently selected from the group consisting of an isononyl group and a 2-propylheptyl group.
[Claim 6]
The plasticizer composition of claim 1 , wherein the plasticizer composition further comprises an additive plasticizer, wherein the additive plasticizer is selected from an epoxidized oil and a trimellitate-based material.
[Claim 7]
The method according to claim 6, wherein the epoxidized oil is epoxidized soybean oil, epoxidized castor oil, epoxidized linseed oil, epoxidized palm oil, epoxidized A plasticizer composition that is at least one selected from the group consisting of stearate (epoxidized stearate), epoxidized oleate (epoxidized oleate), epoxidized tall oil (epoxidized tall oil) and epoxidized linoleate (epoxidized linoleate).
[Claim 8]
The method according to claim 6, wherein the trimellitate-based material is at least one selected from the group consisting of tri(2-ethylhexyl) trimellitate, triisononyl trimellitate and tri(2-propylheptyl) trimellitate. Phosphorus plasticizer composition.
[Claim 9]
The plasticizer composition according to claim 6, wherein the weight ratio of the total weight of the cyclohexane-1,2-diester-based material and diisononyl terephthalate to the total weight of the additional plasticizer is 90:10 to 30:70.
[Claim 10]
The plasticizer composition according to claim 6, wherein the weight ratio of the total weight of the cyclohexane-1,2-diester-based material and diisononyl terephthalate to the total weight of the additional plasticizer is 80:20 to 50:50.
[Claim 11]
100 parts by weight of resin; and 5 to 150 parts by weight of the plasticizer composition according to claim 1 .
[Claim 12]
The method according to claim 11, wherein the resin is straight vinyl chloride polymer, paste vinyl chloride polymer, ethylene vinyl acetate copolymer, ethylene polymer, propylene polymer, polyketone, polystyrene, polyurethane, natural rubber, synthetic rubber and from the group consisting of a thermoplastic elastomer One or more selected resin compositions.