[One]Cross Citation with Related Applications
[2]
This application claims the benefit of priority based on Korean Patent Application No. 10-2019-0051717 dated May 02, 2019, 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 comprising two or more types of isophthalate having the same carbon number and one or more types having different carbon atoms as isophthalate, and a resin composition including the same.
[6]
background
[7]
Plasticizers typically react with alcohols with polycarboxylic acids such as phthalic acid and adipic acid to form the corresponding esters. In addition, in consideration of domestic and international regulations on phthalate-based plasticizers harmful to the human body, research on plasticizer compositions that can replace phthalate-based plasticizers such as isophthalate-based, adipate-based, and other polymer-based plasticizers is continuing.
[8]
[9]
On the other hand, regardless of the plastisol industry such as flooring, wallpaper, soft and hard sheet, calendaring industry, and extrusion/injection compound industry, the demand for these eco-friendly products is increasing, and the quality characteristics, processability and In order to enhance productivity, an appropriate plasticizer should be used in consideration of discoloration, transferability, and mechanical properties.
[10]
In these various areas of use, additives such as plasticizers, fillers, stabilizers, viscosity reducing agents, dispersants, defoamers, foaming agents, etc. will do
[11]
For example, among the plasticizer compositions applicable to PVC, when di(2-ethylhexyl) isophthalate (DEHIP), which is relatively inexpensive and most commonly used, is applied, the hardness or sol viscosity is high and the absorption rate of the plasticizer is high is relatively slow, and the transferability and stress transferability were not good.
[12]
As an improvement to this, as a composition containing DEHIP, it may be considered to apply the product of the transesterification reaction with butanol as a plasticizer, but the plasticization efficiency is improved, but the heating loss and specific gravity are poor, and the mechanical properties are poor There is currently no solution other than adopting a method that compensates for this through mixing with other secondary plasticizers as physical properties are required to be improved, such as slightly lowered.
[13]
However, when the secondary plasticizer is applied, it is difficult to predict the change in physical properties, and it may act as a factor in increasing the unit price of the product, and the research progresses slowly, such as the improvement of the physical properties is not evident except in certain cases.
[14]
DETAILED DESCRIPTION OF THE INVENTION
technical challenge
[15]
The present invention is a plasticizer composition comprising two or more types having the same type of carbon number as isophthalate and at least one type having a different number of carbon atoms. An object of the present invention is to provide a plasticizer composition that can improve viscosity stability, migration loss and stress resistance while maintaining and improving plasticization efficiency, heat loss, and mechanical properties at equal or higher levels compared to existing plasticizers.
[16]
means of solving the problem
[17]
According to one embodiment of the present invention in order to solve the above problems, as isophthalate, the same type of carbon number of the alkyl group bonded to the two ester groups is the same as each other; two or more types are included, and isophthalate bonded to the two ester groups Including one or more types of different carbon number types in the alkyl group, the different carbon number types include both higher alkyl and lower alkyl, and the higher alkyl has 8 to 10 carbon atoms, and the lower alkyl has 8 to 10 carbon atoms. It is selected from 5 to 7, and the difference in carbon number between the higher alkyl and the lower alkyl is 3 or less.
[18]
According to another embodiment of the present invention in order to solve the above problems, 100 parts by weight of the resin; And 5 to 150 parts by weight of the above-mentioned plasticizer composition; is provided a resin composition comprising.
[19]
The resin is 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. can
[20]
Effects of the Invention
[21]
The plasticizer composition according to an embodiment of the present invention, when used in a resin composition, maintains and improves plasticization efficiency, heat loss and mechanical properties at equal or higher levels compared to existing plasticizers, and at the same time, viscosity stability, migration loss and stress resistance can be improved
[22]
Modes for carrying out the invention
[23]
The terms or words used in the present specification and claims should not 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.
[24]
[25]
Definition of Terms
[26]
The term "composition" as used herein includes reaction products and decomposition products formed from materials of the composition, as well as mixtures of materials comprising the composition.
[27]
The term "polymer," as used herein, refers to a polymer compound prepared by polymerizing monomers, whether of the same or a different type. The generic term polymer thus encompasses the term homopolymer, which is commonly used to refer to polymers prepared from only one monomer, and the term interpolymer, as defined below.
[28]
The term "interpolymer," as used herein, refers to a polymer prepared by the polymerization of at least two different monomers. As such, the generic term interpolymer includes copolymers, which are commonly used to refer to polymers prepared from two different monomers, and polymers prepared from two or more different monomers.
[29]
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. 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, including.
[30]
As used herein, "the same type of carbon number" and "the type with different carbon numbers" are terms that distinguish isophthalate, and "the same type of carbon number" refers to an alkyl group bonded to two ester groups of isophthalate, regardless of symmetry and asymmetry. It means that the number of carbons is the same as each other, and "different carbon number type" means that the number of carbon atoms of the alkyl groups bonded to two ester groups of isophthalate is different from each other.
[31]
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 tens to 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.
[32]
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, etc., It refers to a polymer having a size of several thousand nanometers and has poor flowability as fine, dense void-free particles.
[33]
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 is not essential to operability. The term 'consisting of' excludes any component, step or procedure not specifically described or listed.
[34]
[35]
How to measure
[36]
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).
[37]
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.
[38]
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.
[39]
[Equation 1]
[40]
Tensile strength (kgf/cm 2 ) = load value (kgf) / thickness (cm) x width (cm)
[41]
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.
[42]
[Equation 2]
[43]
Elongation (%) = length after stretching / initial length x 100
[44]
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 glass plate to both sides of the test piece, and then 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 glass plate attached to both sides of the test piece, measure the weight before and after leaving the glass plate and the specimen plate in the oven to calculate the transfer loss by Equation 3 below.
[45]
[Equation 3]
[46]
Transition loss (%) = {[(initial weight of specimen) - (weight of specimen after leaving in oven)] / (weight of initial specimen)} x 100
[47]
In the present specification, 'volatile loss' refers to measuring the weight of the specimen after working the specimen at 80°C for 72 hours.
[48]
[Equation 4]
[49]
Loss on heating (%) = {[(initial specimen weight) - (test specimen weight after work)] / (initial specimen weight)} x 100
[50]
In the present specification, the 'absorption rate' is evaluated by measuring the time it takes for the resin and the plasticizer to be mixed with each other and the torque of the mixer is stabilized using a planatary mixer (Brabender, P600) under the conditions of 77°C and 60rpm. do.
[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 different cases, 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]
According to an embodiment of the present invention, the plasticizer composition includes two or more kinds of isophthalate, the same type of carbon number of the alkyl group bonded to the two ester groups as isophthalate, and the number of carbon atoms of the alkyl group bonded to the two ester groups as isophthalate. includes at least one type with different carbon number different from each other, and the type with different carbon number includes both higher alkyl and lower alkyl, wherein the higher alkyl has 8 to 10 carbon atoms, and the lower alkyl has 5 to 7 carbon atoms. is selected from
[55]
[56]
According to one embodiment of the present invention, the plasticizer composition includes the same type of carbon number of the alkyl group bonded to the two ester groups having the same number of carbon atoms, and two or more isophthalates of the same type with the same number of carbon atoms.
[57]
In the case of the type having the same number of carbon atoms, it means that the alkyl groups bonded to two ester groups present in the isophthalate are identical to each other and have alkyl groups having the same number of carbon atoms as the center of the benzene ring, where the two types of isophthalate having the same number of carbon atoms is classified into a higher alkyl isophthalate and a lower alkyl isophthalate having a large number of carbon atoms, and may be included at the same time.
[58]
The same type of carbon number is an alkyl group bonded to two ester groups, n-pentyl, isopentyl, n-hexyl, isohexyl, n-heptyl, isoheptyl, 2-ethylhexyl, isononyl, isodecyl or 2-propylheptyl. tyl, wherein those which may be classified as lower alkyl may be n-pentyl, isopentyl, n-hexyl, isohexyl, n-heptyl and isoheptyl having 5 to 7 carbon atoms. Also, those that can be classified as higher alkyl may be 2-ethylhexyl, isononyl, isodecyl and 2-propylheptyl having 8 to 10 carbon atoms. Here, when the carbon number of the higher alkyl is less than 8, mechanical properties are deteriorated, and at the same time, there is a possibility that the heating loss and stress resistance are deteriorated. It can have a great impact on productivity degradation, and the plasticization efficiency may also deteriorate, and physical properties of a poor level may appear in migration resistance and stress resistance.
[59]
More specifically, the isopentyl, isohexyl and isoheptyl are substituents in which a methyl group or an ethyl group is branched to the main chain, for example, isopentyl is 2-methylbutyl, 2,2-dimethylpropyl, 3-methylbutyl, etc. may include any one or more of the branched structural isomers of C5, wherein isohexyl is 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 2-ethylbutyl, 2,2-dimethylbutyl and 2,3 - May include any one or more of C6 branched structural isomers such as dimethylbutyl, and isoheptyl is 2-methylhexyl, 3-methylhexyl, 4-methylhexyl, 5-methylhexyl, 2-ethylpentyl, 3 -Ethylpentyl, 4-ethylpentyl, 2,3-dimethylpentyl, etc. may include any one or more of C7 branched structural isomers. Here, if the carbon number of the lower alkyl is less than 5, there is a risk of poor heating loss with deterioration of mechanical properties. .
[60]
The difference in carbon number between the alkyl groups that can be bonded to the lower alkyl isophthalate and the alkyl groups that can be bonded to the higher alkyl isophthalate is 3 or less, and each of the higher alkyl and the lower alkyl is selected. As such, when the difference in carbon number between the lower and higher alkyls is 3 or less, the plasticization efficiency is maintained and improved at the same level or higher when applied to a resin compared to that having a carbon number difference of 4, but excellent effects can be seen in transferability and stress resistance.
[61]
In addition, in another aspect, compared to those having a carbon number difference of 4 or more, viscosity stability when applied to a resin may be significantly excellent, and the effect of improving tensile strength and elongation as well as transferability may be excellent.
[62]
In addition to the characteristics of the same type of carbon number as described above, in order to achieve the above effect, an isophthalate of a different carbon number type must also be included, and at this time, the number of carbon atoms of the alkyl bonded to two ester groups of the isophthalate of the different carbon number type The difference may be 3 or less.
[63]
Here, the two alkyl groups bonded to the ester group of the isophthalate having a different carbon number may be the same as the alkyl group of the lower alkyl isophthalate and the higher alkyl isophthalate having the same type of carbon number, respectively. When a carbon number different type of isophthalate is included, the above-described effect may be realized.
[64]
Specifically, the isophthalate of the same type having the same carbon number is, for example, di(2-propylheptyl) isophthalate, diisodecyl isophthalate, isodecyl (2-propylheptyl) isophthalate, diisononyl isophthalate, di(2- Ethylhexyl) isophthalate, di(n-pentyl) isophthalate, diisopentyl isophthalate, (n-pentyl) (isopentyl) isophthalate, di(n-hexyl) isophthalate, diisohexyl isophthalate, isohexyl (n-hexyl) isophthalate, di(n-heptyl) isophthalate, diisoheptyl isophthalate, and isoheptyl (n-heptyl) isophthalate may be selected from the group consisting of isophthalate.
[65]
In addition, in the case of the same type of carbon number, the carbon number of the mutual alkyl group may be the same as well as the structure. have.
[66]
This type of isophthalate having the same number of carbon atoms is, for example, isodecyl (2-propylheptyl) isophthalate, isohexyl (n-hexyl) isophthalate, isoheptyl (n-heptyl) isophthalate, (n-pentyl) (isopentyl) ) may be isophthalate.
[67]
In addition, the type of isophthalate with different carbon number is, for example, (n-pentyl) (2-ethylhexyl) isophthalate, (isopentyl) (2-ethylhexyl) isophthalate, (2-methylbutyl) (2-ethylhexyl) Isophthalate, (n-hexyl) (2-ethylhexyl) isophthalate, isohexyl (2-ethylhexyl) isophthalate, (n-heptyl) (2-ethylhexyl) isophthalate, isoheptyl (2-ethylhexyl) Isophthalate, (n-pentyl) (isononyl) isophthalate, (isopentyl) (isononyl) isophthalate, (n-hexyl) (isononyl) isophthalate, isohexyl (isononyl) isophthalate, (n- Heptyl) (isononyl) isophthalate, isoheptyl (isononyl) isophthalate, (n-pentyl) (isodecyl) isophthalate, (isopentyl) (isodecyl) isophthalate, (n-hexyl) (isodecyl) Isophthalate, isohexyl (isodecyl) isophthalate, (n-heptyl) (isononyl) isophthalate, isoheptyl (isodecyl) isophthalate, (n-pentyl) (2-propylheptyl) isophthalate, (isopentyl) ) (2-propylheptyl) isophthalate, (n-hexyl) (2-propylheptyl) isophthalate, isohexyl (2-propylheptyl) isophthalate, (n-heptyl) (2-propylheptyl) isophthalate, iso It may be selected from the group consisting of heptyl (2-propylheptyl) isophthalate.
[68]
[69]
The plasticizer composition according to an embodiment of the present invention includes a type having the same carbon number and a different carbon number as the isophthalate as described above, but the number of isophthalates of each type, the type of the bonded alkyl group, between the bonded alkyl groups Due to factors such as the difference in carbon number, it is possible to improve physical properties such as migration resistance and stress resistance, and furthermore, the viscosity stability of the resin can be improved, and the plasticizing effect and mechanical properties are also maintained to a level that exceeds the level compared to existing products. and improvement.
[70]
According to an embodiment of the present invention, the plasticizer composition may have a water content of 500 ppm or less based on the total weight of the composition, preferably 300 ppm or less, and more preferably 100 ppm or less. When the water content in the plasticizer is high, the plasticizer is highly likely to be deteriorated by environmental factors, and is likely to cause problems during processing. Therefore, the lower the moisture content in the plasticizer, the better.
[71]
[72]
According to one embodiment of the present invention, the isophthalate of the same type of carbon number and the type of isophthalate having different carbon number included in the plasticizer composition may be included in a weight ratio of 95:5 to 30:70. When included in the above range, it is possible to achieve the aforementioned improvement effects such as migration resistance, stress resistance and viscosity stability, as well as improvement in mechanical properties and plasticization efficiency can be expected.
[73]
More specifically, if the isophthalate included in the plasticizer composition is viewed as a lower alkyl isophthalate, an isophthalate of a different carbon number, and a higher alkyl isophthalate as three types, each is 0.5 to 50% by weight, 3.0 to 70% by weight relative to the total weight of the plasticizer composition % and 0.5 to 85% by weight, these contents are a value when the total of the three types of isophthalates is viewed as 100% by weight, and the content is not considered until other materials are included in the plasticizer composition.
[74]
In the case of having the above content, as described above, the effect that can be realized from the difference in the number of carbon atoms of the alkyl group bonded to the isophthalate of the different type of carbon number is 3 or less can be more preferably realized, and the reproducibility of the effect is also excellent. can
[75]
Further, in terms of optimizing this effect, the content of the three isophthalates may be preferably 0.5 to 50% by weight, 10 to 50% by weight, and 35 to 80% by weight.
[76]
[77]
The method for preparing a plasticizer composition according to an embodiment of the present invention is a method known in the art, and may be applied without particular limitation if it can prepare the above-described plasticizer composition.
[78]
In particular, in the case of the plasticizer composition, including three types of isophthalates as a basis, an esterification reaction may be used, and both a direct esterification reaction and a transesterification reaction may be applied.
[79]
In one example, the direct esterification reaction comprises the steps of adding isophthalic acid and two or more alcohols, then adding a catalyst and reacting in a nitrogen atmosphere; removing unreacted alcohol and neutralizing unreacted acid; and dehydration and filtration by vacuum distillation.
[80]
The alcohol may include at least one lower alkyl alcohol selected from the group consisting of n-pentyl alcohol, isopentyl alcohol, n-hexyl alcohol, isohexyl alcohol, n-heptyl alcohol and isoheptyl alcohol, and the higher alkyl alcohol includes At least one selected from 2-ethylhexyl alcohol, isononyl alcohol, isodecyl alcohol and 2-propylheptyl alcohol may be applied. The alcohol may be used within the range of 150 to 500 mol%, 200 to 400 mol%, 200 to 350 mol%, 250 to 400 mol%, or 270 to 330 mol% based on 100 mol% of isophthalic acid.
[81]
The catalyst is, for example, an acid catalyst such as sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid, para-toluenesulfonic acid, methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, alkyl sulfuric acid, aluminum lactate, lithium fluoride, potassium chloride, cesium chloride, calcium chloride, It may be at least one selected from metal salts such as iron chloride and aluminum phosphate, metal oxides such as heteropolyacids, natural/synthetic zeolites, cation and anion exchange resins, tetraalkyl titanate and organometallics such as polymers thereof. As a specific example, the catalyst may be tetraalkyl titanate.
[82]
The amount of catalyst used may vary depending on the type, for example, in the case of a homogeneous catalyst, 0.01 to 5% by weight, 0.01 to 3% by weight, 1 to 5% by weight, or 2 to 4% by weight based on 100% by weight of the total reactants. and in the case of a heterogeneous catalyst, it may be in the range of 5 to 200 wt%, 5 to 100 wt%, 20 to 200 wt%, or 20 to 150 wt% of the total amount of reactants.
[83]
At this time, the reaction temperature may be in the range of 180 to 280 ℃, 200 to 250 ℃, or 210 to 230 ℃.
[84]
In another example, the transesterification reaction is an alcohol having an alkyl group corresponding to a lower alkyl and a higher alkyl isophthalate of the same carbon number as di(2-ethylhexyl) isophthalate, and a transester in which the lower alkyl alcohol reacts. An isophthalate compound can be prepared through a chemical reaction. Here, the alkyl group of the isophthalate and the alcohol may cross each other, and when two or more types of alcohol are used in the transesterification reaction, the reaction product may be a total of 6 types of isophthalates, for example, the number of carbon atoms is the same. Four types and two types of different carbon number types may be formed, and the same carbon number type may include three types of lower alkyl isophthalate and one type of higher alkyl isophthalate.
[85]
As used in the present invention, "transesterification reaction" refers to a reaction in which an alcohol and an ester are reacted as shown in Scheme 1 below, and as shown in Scheme 1 below, R of the ester is interchanged with R' of the alcohol:
[86]
[Scheme 1]
[87]

[88]
According to an embodiment of the present invention, when the transesterification reaction is performed, when the alkoxide of alcohol attacks the carbons of two ester (RCOOR") groups present in the ester-based compound; attacking the carbon of the ester (RCOOR") group; In the case of unreacted, unreacted; in the three cases, three types of ester compositions can be produced by number.
[89]
In addition, the transesterification reaction has the advantage of not causing a wastewater problem compared to the acid-alcohol esterification reaction, and since it can be carried out in the absence of a catalyst, it is possible to solve the problem when using an acid catalyst.
[90]
In the mixture prepared by the transesterification reaction, the composition ratio of the mixture may be controlled according to the amount of alcohol added. The amount of the alcohol added may be 0.1 to 89.9 parts by weight, specifically 3 to 50 parts by weight, and more specifically 5 to 40 parts by weight based on 100 parts by weight of the isophthalate compound.
[91]
As for the isophthalate compound, the greater the amount of alcohol is added, the greater the mole fraction of isophthalate participating in the transesterification reaction will increase. Correspondingly, the content of unreacted isophthalate may tend to decrease.
[92]
According to an embodiment of the present invention, the molar ratio of the reactant isophthalate and alcohol is, for example, 1:0.005 to 5.0, 1:0.05 to 2.5, or 1:0.1 to 1.0, and within this range, fairness and economic feasibility may be excellent. There is an effect of obtaining a plasticizer composition that can implement the above-described effect.
[93]
According to an embodiment of the present invention, the transesterification reaction is carried out at a reaction temperature of 120° C. to 190° C., preferably 135° C. to 180° C., more preferably 141° C. to 179° C. for 10 minutes to 10 hours, preferably Preferably, it is carried out in 30 minutes to 8 hours, more preferably in 1 to 6 hours. Within the above temperature and time range, it is possible to efficiently control the component ratio of the final plasticizer composition. In this case, the reaction time may be calculated from the point at which the reaction temperature is reached after the reactant is heated.
[94]
The transesterification reaction may be carried out under an acid catalyst or a metal catalyst, and in this case, the reaction time is shortened.
[95]
The acid catalyst may be, for example, sulfuric acid, methanesulfonic acid or p-toluenesulfonic acid, and the metal catalyst may be, for example, an organometallic catalyst, a metal oxide catalyst, a metal salt catalyst, or a metal itself.
[96]
The metal component may be, for example, any one selected from the group consisting of tin, titanium, and zirconium, or a mixture of two or more thereof.
[97]
In addition, the method may further include removing unreacted alcohol and reaction by-products by distillation after the transesterification reaction. The distillation may be, for example, a two-step distillation in which the alcohol and the reaction by-products are separated using a difference in boiling point. In another example, the distillation may be mixed distillation. In this case, there is an effect of relatively stably securing the ester-based plasticizer composition in a desired composition ratio. The mixed distillation means simultaneously distilling unreacted alcohol and reaction by-products.
[98]
[99]
According to another embodiment of the present invention, there is provided a resin composition comprising the above-described plasticizer composition and resin.
[100]
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.
[101]
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.
[102]
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.
[103]
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 a fine resin particle prepared by emulsion polymerization, etc., and such a vinyl chloride polymer is called a paste vinyl chloride resin.
[104]
In this case, 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
[105]
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.
[106]
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.
[107]
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.
[108]
The stabilizer may include, for example, a calcium-zinc (Ca-Zn-based) stabilizer or a barium-zinc-based (Ba-Zn-based) stabilizer such as a calcium-zinc complex stearate salt, but is not particularly limited thereto. it is not
[109]
The resin composition may be applied to both melt processing and plastisol processing as described above, for example, melt processing may include calendering processing, extrusion processing, or injection processing, and plastisol processing may include coating processing, etc. This can be applied.
[110]
[111]
Example
[112]
Hereinafter, examples will be given to describe the present invention in detail. However, the embodiments according to the present invention may be modified in various other forms, and the scope of the present invention should not be construed as being limited to the embodiments described in detail below. The embodiments of the present invention are provided to more completely explain the present invention to those of ordinary skill in the art.
[113]
[114]
Example 1
[115]
2000 g of di(2-ethylhexyl) isophthalate (GL300, LG Chem) and 340 g of n-pentyl alcohol (17 parts by weight based on 100 parts by weight of DEHIP) were added to a reactor equipped with a stirrer, condenser and decanter, and then nitrogen Trans-esterification reaction was carried out for 2 hours at a reaction temperature of 160° C. under an atmosphere, and di(n-pentyl) isophthalate (DnPIP), (n-pentyl) (2-ethylhexyl) isophthalate (nPEHIP) and di(2 -Ethylhexyl) isophthalate (DEHIP) was obtained in a composition comprising 3.6 wt%, 31.7 wt%, and 64.7 wt%, respectively.
[116]
[117]
Examples 2 to 7
[118]
A three-component composition having the weight ratio shown in Table 1 was obtained by reacting in the same manner as in Example 1, except that the alcohol corresponding to the lower alkyl shown in Table 1 was applied instead of n-pentyl alcohol.
[119]
[120]
Example 8
[121]
The reaction was carried out in the same manner as in Example 1, except that n-hexyl alcohol was used instead of n-pentyl alcohol and diisononyl terephthalate was used instead of di(2-ethylhexyl) terephthalate to obtain the weight ratios shown in Table 1 below. Eggplant obtained a three-component composition.
[122]
[123]
Comparative Example 1
[124]
As a product of LG Chem, diisononyl phthalate (DINP) was used as a plasticizer composition.
[125]
[126]
Comparative Example 2
[127]
As a product of LG Chem, di(2-ethylhexyl) terephthalate (DEHTP, LGflex GL300) was used as a plasticizer composition.
[128]
[129]
Comparative Examples 3 to 7
[130]
An alcohol corresponding to the lower alkyl shown in Table 1 was used instead of n-pentyl alcohol, and a dialkyl terephthalate to which an alkyl corresponding to the higher alkyl shown in Table 1 was bonded instead of di(2-ethylhexyl) terephthalate was used. A three-component composition having the weight ratios shown in Table 1 below was obtained by reacting in the same manner as in Example 1 except that.
[131]
[132]
[Table 1]
　　 lower alkyl higher alkyl low-level heterosexuality concoction advanced unmarried
Example 1 n-pentyl 2-ethylhexyl 3.6 31.7 64.7
Example 2 2-methylbutyl 2-ethylhexyl 2.5 27.4 70.1
Example 3 n-hexyl 2-ethylhexyl 4.1 32.2 63.7
Example 4 2-ethylbutyl 2-ethylhexyl 4.2 32.9 62.9
Example 5 n-heptyl 2-ethylhexyl 7.8 40.0 52.2
Example 6 5-methylhexyl 2-ethylhexyl 8.0 41.1 50.9
Example 7 n-pentyl 2-ethylhexyl 6.5 39.5 54.0
Example 8 n-hexyl isononyl 12.3 42.7 45.0
Comparative Example 3 n-butyl 2-ethylhexyl 6.0 38.1 55.9
Comparative Example 4 n-pentyl isononyl 7.4 39.5 53.1
Comparative Example 5 2-ethylhexyl 2-propylheptyl 41.2 46.1 12.7
Comparative Example 6 n-butyl n-heptyl 4.8 32.0 63.2
Comparative Example 7 2-methylbutyl n-heptyl 5.8 38.5 55.7
[133]
* All of the above contents are in weight %.
[134]
[135]
Experimental Example: Performance Evaluation
[136]
Using the plasticizers of Examples and Comparative Examples, specimens were manufactured under the following prescription and manufacturing conditions according to ASTM D638.
[137]
(1) Prescription : 100 parts by weight of straight vinyl chloride polymer (LS100S), 30 parts by weight of plasticizer and 3 parts by weight of stabilizer (BZ-153T)
[138]
(2) Mixing : Mixing at 700 rpm at 98℃
[139]
(3) Specimen production : 1T and 3T sheets were produced by using a roll mill at 160°C for 4 minutes and pressing at 180°C for 2.5 minutes (low pressure) and 2 minutes (high pressure).
[140]
(4) Evaluation items
[141]
1) Hardness : Using ASTM D2240, the shore hardness (Shore "A" and "D") at 25 ℃ was measured for 10 seconds with a 3T specimen. It is evaluated that the plasticizing efficiency is excellent, so that a numerical value is small.
[142]
2) Tensile strength : After pulling the crosshead 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:
[143]
Tensile strength (kgf/cm 2 ) = load value (kgf) / thickness (cm) x width (cm)
[144]
3) Measurement of elongation rate : According to the 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 measured Calculated as follows:
[145]
Elongation (%) = length after stretching / was calculated as initial length x 100.
[146]
4) Measurement of migration loss : After attaching a glass plate to both sides of a 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, after removing the glass plate attached to both sides of the test piece, the weight before and after leaving the glass plate and the specimen plate in the oven was measured to calculate the transfer loss by the following formula.
[147]
Transition loss (%) = {[(initial weight of specimen) - (weight of specimen after leaving in oven)] / (weight of initial specimen)} x 100
[148]
5) Measurement of volatile loss : After working the prepared specimen at 80° C. for 72 hours, the weight of the specimen was measured.
[149]
Loss on heating (%) = {[(initial specimen weight) - (test specimen weight after work)] / (initial specimen weight)} x 100.
[150]
6) Stress test (stress resistance) : After leaving a 2 mm thick specimen in a bent state at 23° C. for 72 hours, observe the degree of transition (the degree of seepage), and display the result as a numerical value (from 0 to 3.0 0.5 unit), and the closer to 0, the better the characteristic.
[151]
7) Measurement of absorption rate
[152]
The absorption rate was evaluated by measuring the time it took for the resin and the ester compound to be mixed with each other and the torque of the mixer was stabilized using a planatary mixer (Brabender, P600) under the conditions of 77° C. and 60 rpm.
[153]
8) Light fastness measurement
[154]
According to the method of ASTM 4329-13, the specimen was placed in QUV (QUV/se, Q-LAB) and UV (340 nm) was irradiated for 200 hours, and then the color change (△ E) was confirmed.
[155]
(5) Evaluation results
[156]
The evaluation results of the above items are shown in Tables 2 and 3 below.
[157]
[Table 2]
　　 Hardness (Shore A) Hardness (Shore D) Tensile strength (kgf/cm 2 ) Elongation (%) Performance loss (%) Heat loss (%)
Example 1 92.5 47.2 256.9 301.2 2.99 1.69
Example 2 92.9 48.6 251.2 294.4 2.91 1.77
Example 3 92.7 48.1 255.5 300.7 3.07 1.14
Example 4 93.2 48.9 263.4 298.0 2.90 1.42
Example 5 93.0 48.4 259.9 294.9 3.11 1.02
Example 6 93.2 48.7 260.4 302.1 3.15 1.10
Example 7 91.6 46.2 267.8 295.8 2.13 1.80
Example 8 93.5 49.2 241.7 290.3 3.54 0.87
Comparative Example 1 93.9 49.7 230.3 280.9 2.32 0.75
Comparative Example 2 94.8 50.1 249.9 301.5 4.57 0.78
Comparative Example 3 91.5 47.3 238.1 289.0 3.87 3.88
Comparative Example 4 94.3 49.9 233.3 290.2 4.32 1.58
Comparative Example 5 95.4 51.8 235.3 302.4 4.30 0.78
Comparative Example 6 90.3 45.5 230.6 284.7 3.53 3.51
Comparative Example 7 90.4 45.7 235.4 288.3 3.65 3.74
[158]
[Table 3]
　　 stress transferability absorption rate light fastness
Example 1 1.0 5m10s 1.05
Example 2 1.0 6m12s 1.07
Example 3 1.0 5m58s 0.98
Example 4 1.0 5m60s 0.85
Example 5 1.5 6m10s 1.02
Example 6 1.5 6m15s 1.12
Example 7 1.0 4m45s 1.10
Example 8 1.0 6m02s 1.00
Comparative Example 1 0.5 4m30s 1.10
Comparative Example 2 3.0 7m56s 3.25
Comparative Example 3 1.0 4m25s 1.14
Comparative Example 4 1.5 5m55s 1.25
Comparative Example 5 3.0 8m26s 1.35
Comparative Example 6 3.0 4m40s 1.01
Comparative Example 7 3.0 4m50s 1.14
[159]
Referring to the results of Tables 2 and 3, the case in which the plasticizer of Examples 1 to 8 was applied showed an excellent effect in most of the physical properties compared to the case where the plasticizer of Comparative Examples 1 to 7 was applied, and it can be confirmed that the balance between the physical properties is excellent. In particular, it can be seen that excellent effects can be seen in tensile strength and elongation, stress resistance, and plasticization efficiency. Furthermore, it can be seen that the absorption rate is not too fast between 4 and 6 minutes, so there is no fear of being discharged, and the processability is also excellent in that it does not exceed 7 minutes. It can be confirmed that there is a significant improvement in mechanical properties even compared to Comparative Example 1, which has significant issues, and compared to Comparative Example 2, which is an existing eco-friendly product, plasticization efficiency, migration loss, and stress resistance and light resistance are very excellent. and it was confirmed that the absorption rate can be improved to an appropriate level.
[160]
In addition, unlike the plasticizer composition according to the present invention, in Comparative Example 3, in which the carbon number difference between the higher alkyl and the lower alkyl is not 3 or less and the lower alkyl carbon number is less than 5, the elongation and the heating loss are particularly inferior, Comparative Example 4, in which the carbon number of the lower alkyl and the higher alkyl was the same as in the present invention, but the difference in carbon number still exceeds 3, as the plasticization efficiency deteriorated, the tensile strength deteriorated together, and it is confirmed that the transition loss is inferior .
[161]
In addition, even if the carbon number difference is satisfied, Comparative Example 5, in which the lower alkyl carbon number is too large, has a significant loss in plasticization efficiency, and the absorption rate is also too slow, so it can be inferred that the processability is very poor. It can be confirmed through Comparative Example 6 that the stress property is also deteriorated, and further, when the lower alkyl carbon number and the lower alkyl carbon number are both small, the tensile strength and elongation, heat loss and stress resistance are very poor. It is confirmed that the same appears in Comparative Example 7, which is a case where the number of carbon atoms is small.

WE CLAIMS

As isophthalate, two or more types of the same type of carbon number of the alkyl group bonded to the two ester groups are the same; and the different carbon number type includes both higher alkyl and lower alkyl, the higher alkyl has 8 to 10 carbon atoms, the lower alkyl has 5 to 7 carbon atoms, and the higher alkyl and lower alkyl carbon number the difference is 3 or less.
[Claim 2]
The plasticizer composition according to claim 1, wherein the same type of carbon number includes a higher alkyl isophthalate having 8 to 10 carbon atoms and a lower alkyl isophthalate selected from 5 to 7 carbon atoms.
[Claim 3]
According to claim 1, wherein the carbon number different type is (n-pentyl) (2-ethylhexyl) isophthalate, (isopentyl) (2-ethylhexyl) isophthalate, (n-hexyl) (2-ethylhexyl) iso Phthalate, isohexyl (2-ethylhexyl) isophthalate, (n-heptyl) (2-ethylhexyl) isophthalate, isoheptyl (2-ethylhexyl) isophthalate, (n-pentyl) (isononyl) isophthalate, (Isopentyl) (isononyl) isophthalate, (n-hexyl) (isononyl) isophthalate, isohexyl (isononyl) isophthalate, (n-heptyl) (isononyl) isophthalate, isoheptyl (isononyl) Isophthalate, (n-pentyl) (isodecyl) isophthalate, (isopentyl) (isodecyl) isophthalate, (n-hexyl) (isodecyl) isophthalate, isohexyl (isodecyl) isophthalate, (n- Heptyl) (isononyl) isophthalate, isoheptyl (isodecyl) isophthalate, (n-pentyl) (2-propylheptyl) isophthalate, (isopentyl) (2-propylheptyl) isophthalate, (n-hexyl) 1 selected from the group consisting of (2-propylheptyl) isophthalate, isohexyl (2-propylheptyl) isophthalate, (n-heptyl) (2-propylheptyl) isophthalate, and isoheptyl (2-propylheptyl) isophthalate A plasticizer composition that is more than one species.
[Claim 4]
The method according to claim 1, wherein the same type having the same number of carbon atoms is di(2-propylheptyl) isophthalate, diisodecyl isophthalate, isodecyl (2-propylheptyl) isophthalate, diisononyl isophthalate, and di(2-ethylhexyl). ) isophthalate, di (n-pentyl) isophthalate, diisopentyl isophthalate, (n-pentyl) (isopentyl) isophthalate, di (n-hexyl) isophthalate, diisohexyl isophthalate, isohexyl (n) -Hexyl) isophthalate, di (n-heptyl) isophthalate, diisoheptyl isophthalate, and isoheptyl (n-heptyl) a plasticizer composition that is at least two selected from the group consisting of isophthalate.
[Claim 5]
The plasticizer composition according to claim 1, wherein the weight ratio of the type having the same number of carbon atoms and the type having the same number of carbon atoms is 95:5 to 30:70.
[Claim 6]
According to claim 2, 0.5 to 50% by weight of a lower alkyl isophthalate, based on the total weight of the plasticizer composition; 3.0 to 70% by weight of isophthalate of a different carbon number type; And 0.5 to 85% by weight of higher alkyl isophthalate; plasticizer composition comprising a.
[Claim 7]
100 parts by weight of resin; And 5 to 150 parts by weight of the plasticizer composition of claim 1; A resin composition comprising a.
[Claim 8]
8. The group of claim 7, wherein the resin is a straight vinyl chloride polymer, a paste vinyl chloride polymer, an ethylene vinyl acetate copolymer, an ethylene polymer, a propylene polymer, a polyketone, a polystyrene, a polyurethane, a natural rubber, a synthetic rubber, and a thermoplastic elastomer. A resin composition that is at least one selected from