KR100676942B1 - Plasticizer composition containing cyclodextrin derivatives, flexible pvc composition with suppression of the migration of plasticizer containing the same, and manufacturing method thereof - Google Patents

Abstract

Provided is a plasticizer composition, which contains a cyclodextrin derivative capable of forming a complex with a liquid low-molecular weight plasticizer to prevent the plasticizer from migration, and thus allows mass production of a flexible PVC composition showing little migration of a plasticizer. The flexible PVC composition showing little migration of a plasticizer is obtained by the method comprising the steps of: (S1) providing a cyclodextrin derivative represented by the following formula 3; (S2) mixing the cyclodextrin derivative, PVC and a liquid plasticizer to form plastisol; and (S3) heating the plastisol to a solution state, followed by cooling. In the formula 3, R independently represents any one of a C1-C20 hydrocarbon functional group represented by the following formula 4 and a C1-C60 silane functional group represented by the following formula 5, and has a substitution degree of 5-100%; and n is an integer of 6-26. In the formula 4, each of a, b, c, d and e is an integer of 0 or more, a+b+c+d+e is 1 or more, and the order of each unit varies randomly. In the formula 5, each of R1, R2 and R3 independently represents a C1-C20 hydrocarbon functional group represented by the formula 4.

Description

Plasticizer composition incorporating cyclodextrin derivatives, plasticizer effluent reduced soft PCC composition comprising the same, and a method for preparing the same.Plasticizer composition containing cyclodextrin derivatives, flexible PVC composition with suppression of the migration of plasticizer containing the same, and manufacturing method

1 is a schematic diagram showing the structure of an alpha-cyclodextrin derivative as one embodiment of a cyclodextrin derivative used in the present invention.

FIG. 2 is a schematic diagram schematically illustrating a structure of a cyclodextrin derivative in which a DOP is drawn into a cavity to form a complex in the plasticizer composition of the present invention.

Figure 3 is a schematic diagram showing a simple structure of the plasticizer outflow-type soft PVC composition in which PVC, a liquid low-molecular plasticizer and a cyclodextrin derivative is uniformly mixed according to the present invention.

Figure 4 is a photograph of the surface of the sample (PVC-9) of the sample (PVC-0) of Comparative Example 1 that does not contain a cyclodextrin derivative.

5 is a photograph of the surface of the sample (PVC-9) of Example 4 containing a predetermined amount of cyclodextrin derivatives.

Figure 6 is a photograph of the surface of a sample prepared by dispersing pure beta-cyclodextrin in DMAc solvent according to the prior art.

7 is an absorbance calibration curve of the standard solution prepared for the phthalate plasticizer effluent concentration evaluation,

8 is a graph showing the DOP leakage test results of the plasticizer outflow-type PVC specimens according to the present invention.

9 is a stress-strain curve graph of the plasticizer outflow reduced soft PVC specimen according to the present invention.

The present invention relates to a method for producing a soft PVC by mixing a PVC and a liquid low molecular plasticizer, and more particularly, a plasticizer composition which can reduce the outflow when used as a plasticizer by forming a composite by mixing with a liquid low molecular plasticizer. The present invention relates to a method for producing a plasticizer effluent reduction soft PVC composition comprising the same, and to a plasticizer effluent reduction soft PVC composition formed therefrom.

For example, PVC is a representative general-purpose polymer widely used in pipes, food packaging materials, textile fibers, indoor decorations and blood storage containers, baby products such as baby bottles and toys. However, PVC exhibits rigid properties due to molecular mobility constraints due to the presence of microcrystallites that serve as specific intra- molecular governance structures and physical crosslinks, and thus, for soft applications such as food packaging films. In order to be applied, ductility must be imparted through a plasticization process. Soft PVC is typically prepared by mixing a liquid low molecular plasticizer (PVC) with PVC to form a plastisol, then heating the PVC to dissolve the PVC in a liquid low molecular plasticizer and then cooling. Phthalate-based plasticizers, phosphate-based plasticizers, trimellitate-based plasticizers, aliphatic diester-based plasticizers and the like are well known as liquid low-molecular-weight plasticizers. In addition to these, there are epoxy plasticizers and anti-chlorine plasticizers. Due to the addition of low molecular weight plasticizers, the molecular mobility of PVC is greatly improved, thereby giving ductility to PVC.

As such, the liquid low molecular plasticizer may be very useful for softening of PVC, but has a property of volatilizing into the air or transferring to the outside through contact with a liquid or solid material due to the low molecular weight of the liquid phase. When the plasticizer leaked out of PVC enters the body of animals, animals and plants, it is reported to cause fatal harm by inhibiting the normal activity of endocrine system directly involved in life activities or triggering abnormal reactions.

Therefore, efforts to reduce the external flow rate of the plasticizer are continued.

For example, attempts have been made to substitute polymer plasticizers instead of liquid low molecular plasticizers so that there is no problem of plasticizer leakage from PVC products. However, when the polymer plasticizer is used, there is a problem in that it is not economical or the plasticization performance is insufficient and chain entanglement occurs.

Meanwhile, Journal of Applied Polymer Science, 1996, Vol. 59, P. 2089 According to "Effect of blending β-cyclodextrin with poly (vinyl chloride) on the leaching of phthalate ester to hydrophilic medium", plasticizers of soft PVC are formed by cyclodextrins complexing with liquid low-molecular-weight plasticizers such as DOP. It is reported that it can contribute to the emission reduction.

Like the alpha-cyclodextrin of the formula (1), cyclodextrin is a cyclic compound composed of a glucose group as a repeating unit is represented by the following formula (2).

In Chemical Formula 2, n has an integer of 6 to 26, preferably 6 to 8 as the number of glucose group repeating units.

Cyclodextrins consist of a unique structure of hydrophobic inner cavities and the outside surrounded by hydrophilic hydroxy functional groups. Cyclodextrins can form complexes with plasticizers that are large enough to enter these internal cavities, ie, liquid, low molecular weight plasticizers. Of course, the cyclodextrin derivative not only draws the liquid low molecular plasticizer into the cavity, but also attracts and fixes the liquid low molecular plasticizer by hydrogen bonding to the outside.

However, cyclodextrins mixed with PVC and liquid low molecular weight plasticizers are poor in dispersibility and aggregate with each other, thereby greatly reducing plasticizer outflow reduction ability, and also deteriorating physical properties of the manufactured soft PVC. In the above-mentioned literature, in order to solve this problem, a plasticizer effluent reduced soft PVC was prepared by dispersing PVC, DOP, and cyclodextrin in a dimethylacetamide (DMAc) solvent and then casting. However, this method is not only economical and difficult to apply to mass production, but also does not completely solve the problem of coagulation of cyclodextrin.

Therefore, the technical problem to be achieved by the present invention is to solve the above problems, it is possible to mass-produce in a simple and economical way without using a solvent, and the plasticizer is leaked without substantially deteriorating the physical properties of the produced soft PVC The amount is to provide a process for producing a plasticizer effluent reduced soft PVC composition that is greatly reduced.

Another technical problem to be achieved by the present invention is to form a composite by mixing with a low-molecular plasticizer of the liquid plasticizer composition that can reduce the outflow of the plasticizer without substantially reducing the physical properties when used as a plasticizer of PVC and plasticizer outflow reduction type comprising the same It is to provide a soft PVC composition.

In order to achieve the above technical problem, the method for producing a plasticizer outflow-type soft PVC composition of the present invention (S1) preparing a cyclodextrin derivative represented by the following formula (3); (S2) mixing the cyclodextrin derivative, PVC and a low molecular weight plasticizer in a liquid to form a plastisol; And (S3) heating the formed plastisol to a solution state and then cooling.

In Chemical Formula 3, R is each independently selected from hydrogen, a hydrocarbon functional group having 1 to 20 carbon atoms represented by the following Chemical Formula 4, and a silane functional group having 1 to 60 carbon atoms represented by the following Chemical Formula 5, The degree of substitution of R is 5 to 100% and n is an integer of 6 to 26.

In Formula 4, a, b, c, d and e are each an integer of 0 or more, and a + b + c + d + e is 1 or more, and a combination of each structural unit according to a, b, c, d and e The order of may be randomly modified.

In Formula 5, R ₁ , R ₂ , and R ₃ are each independently a hydrocarbon functional group having 1 to 20 carbon atoms represented by Formula 4.

According to the production method of the present invention, it is possible to mass-produce a plasticizer outflow-reducing type soft PVC in a simple and economical manner without using a solvent, and the produced soft PVC greatly reduces the amount of plasticizer outflow without substantially decreasing physical properties. do.

In the method for producing a plasticizer effluent reduced soft PVC composition of the present invention, the content of the cyclodextrin derivative is preferably 2 to 20 mol based on 100 mol of the low molecular weight plasticizer in the liquid phase.

In the method for preparing a plasticizer-flow-reducing type soft PVC composition of the present invention, the liquid low molecular weight plasticizer includes dimethyl phthalate (DMP), dibutyl phthalate (DBP), and diisobutyl phthalate (di-isobutyl). phthalate (DIBP), dihexyl phthalate (DHP), dioctyl phthalate (DOP), di-iso-octyl phthalate (DIOP), dinonyl phthalate (DNP) , Phthalate plasticizers such as di-isodecyl phthalate (DIDP), benzyl butyl phthalate (BBP), dioctyl adipate (DOA), di-octyl adipate (di-isodecyl phthalate) aliphatic diester plasticizers such as -octyl adipate (DIOA), di-isodecyl adipate (DIDA), triiso octyl trimellitate (tri-i) trimellitate plasticizers such as so-octyl trimellitate (TIOTM), phosphate plasticizers such as tritolyl phosphate (TTP), trixylyl phosphate (TXP), etc., alone or in combination It can be mixed and used.

Hereinafter, the manufacturing method of the plasticizer outflow type reduced soft PVC composition of this invention is demonstrated in detail.

First, a cyclodextrin derivative represented by Chemical Formula 3 is prepared (step S1).

[Formula 3]

In Formula 3, R may be each independently hydrogen, a hydrocarbon group having 1 to 20 carbon atoms represented by Formula 4, or a silane group having 1 to 60 carbon atoms represented by Formula 5 below. n is an integer of 6-26, Preferably it is an integer of 6-8. The degree of substitution of R is 5 to 100%, preferably 20 to 90%, and the degree of substitution is calculated according to Equation 1 as follows.

Degree of substitution = (total number of hydroxyl groups subjected to substitution reaction / total number of hydroxy groups present in cyclodextrin) X 100 (%)

[Formula 4]

In Formula 4, a, b, c, d and e are each an integer of 0 or more, and a + b + c + d + e is 1 or more. That is, the order of bonding between the constituent units according to a, b, c, d, and e is not limited to the arrangement order represented by Formula 4, and may be modified randomly. Examples of the hydrocarbon functional group represented by the formula (4) include methyl, ethyl, butyl, octyl, decyl, hexadecyl, aryl, phenyl, benzyl, and the like, but are not limited thereto.

[Formula 5]

In Formula 5, R ₁ , R ₂ , and R ₃ are each independently a hydrocarbon functional group having 1 to 20 carbon atoms represented by Formula 4. Examples of the silane-based functional group represented by the formula (5) include trimethyl silane, butyldimethyl silane, methoxy silane, ethoxy silane, methacryloxypropyl methoxy silane, and the like, but are not limited thereto.

Such cyclodextrin derivatives may be prepared by reacting the cyclodextrin represented by Chemical Formula 2 with the compound represented by the following Chemical Formula 6.

In Chemical Formula 6, R is the same as R in Chemical Formula 3, and X is a functional group capable of reacting with the hydroxyl group of the cyclodextrin represented by Chemical Formula 2, for example, a halogen element, a hydroxyl group, an alkoxy group, or the like. Can be mentioned. By this substitution reaction, the hydrogen atom of the hydroxy group in the cyclodextrin is replaced with R. According to the number of moles of the compound represented by Formula 6 during the substitution reaction, the degree to which the hydrogen atom is substituted with R, that is, the degree of substitution may be adjusted.

Subsequently, the prepared cyclodextrin derivative, PVC, and a liquid low molecular weight plasticizer are mixed to form a plastisol (step S2).

The cyclodextrin derivative of Formula 3, in which a hydrogen functional group is substituted with a predetermined compound, has a good dispersibility when mixed with PVC and a low molecular weight plasticizer in a liquid, unlike pure cyclodextrin of Formula 2. Therefore, it is possible to form a plastisol in which the cyclodextrin derivative is uniformly dispersed without using a solvent such as DMAc as in the related art. Accordingly, there is an advantage that can be mass-produced plasticizer outflow-type soft PVC simply and economically.

The mixed amount of the cyclodextrin derivative is preferably 2 to 20 mol when the mixed amount of the low molecular weight plasticizer in the liquid is 100 mol.

In addition, any liquid low-molecular plasticizer used can be used as long as it can form a complex through the internal cavity of the cyclodextrin derivative, considering the size of the internal cavity of the cyclodextrin derivative is a common used for softening of PVC Liquid low molecular plasticizers such as dimethyl phthalate (DMP), dibutyl phthalate (DBP), di-isobutyl phthalate (DIBP), dihexyl phthalate (DHP), Dioctyl phthalate (DOP), di-iso-octyl phthalate (DIOP), dinonyl phthalate (DNP), di-isodecyl phthalate (DIDP), benzyl butyl Phthalate plasticizers such as phthalate (benzyl butyl phthalate, BBP), dioctyl adipate (DOA), Aliphatic diester plasticizers such as di-iso-octyl adipate (DIOA), di-isodecyl adipate (DIDA), tri-iso-octyl trimellitate , Phosphate plasticizers such as trimellitate plasticizers such as TIOTM), tritolyl phosphate (TTP), trixylyl phosphate (TXP), etc., alone or in combination of one or more thereof. Can be. It is apparent to those skilled in the art that the mixing ratio of the PVC and the liquid low molecular weight plasticizer can be changed according to the degree of ductility to be given, for example, 10 to 80 parts by weight of the plasticizer is mixed based on 100 parts by weight of PVC.

In the above-described step S2, the cyclodextrin derivative may be mixed with PVC and the low molecular weight plasticizer at the same time to form a plastisol, but the cyclodextrin derivative and the low molecular weight plasticizer are first mixed to form a plasticizer composition, which is then It can also be mixed with PVC to form a plastisol. That is, according to the present invention, a plasticizer composition comprising a cyclodextrin derivative and a liquid low molecular weight plasticizer may be first formed, and then used instead of the plasticizer of PVC which is commonly used.

Finally, the formed plastisol is heated until it is in solution and then cooled (step S3).

Plastisol formed by adding a cyclodextrin derivative of Formula 3 to a soft PVC composition containing PVC and a low molecular weight plasticizer in liquid form becomes a solution in which other components are dissolved in a low molecular weight plasticizer, for example. Cooling it produces a plasticizer effluent reduced soft PVC composition in which all components, namely PVC, low molecular weight plasticizers and cyclodextrin derivatives are uniformly mixed.

Looking at the principle that the outflow of the plasticizer is reduced in the produced plasticizer outflow-type soft PVC composition is as follows.

1 is a schematic diagram showing the structure of an alpha-cyclodextrin derivative as one embodiment of a cyclodextrin derivative used in the present invention. Referring to the drawings, the alpha-cyclodextrin derivative is a structure having a cavity inside. Such cyclodextrin derivatives attract liquid low molecular plasticizers, such as DOP, into the cavity to form a complex, thereby preventing the plasticizer from spilling (see FIG. 2). That is, as shown in Figure 3, according to the present invention, a plasticizer effluent reduced type soft PVC composition in which PVC, a low molecular weight plasticizer and a cyclodextrin derivative is uniformly mixed according to the present invention, the cyclodextrin derivatives form a complex with DOP efficiently Reduction efficiency for the outflow is improved, and the physical properties are hardly reduced.

  Hereinafter, examples will be described in detail to help understand the present invention. However, embodiments according to the present invention can be modified in many different forms, the scope of the invention should not be construed as limited to the following examples. Embodiments of the present invention are provided to more fully describe the present invention to those skilled in the art.

Synthesis Example 1

This synthesis example is intended to illustrate the synthesis of the cyclodextrin derivative represented by the following formula (7) by reacting beta-cyclodextrin with benzyl chloride.

Synthesis of 2,3,6-tri- O -benzyl-beta-cyclodextrin (hereinafter referred to as Bn-β-CD) represented by Chemical Formula 7 is described in Carbohydrate Research 1990, Vol. 199, P. 31-35 "Synthesis of 1,4-anhydro-2,3,6-tri- O- benzyl-α-D-glucopyranose by cis -ring-closure of a glycosyl chloride" .

Beta-cyclodextrin used for the reaction was purchased from Tokyo Kasei. 5.0 g of beta-cyclodextrin was dissolved in 250 ml of dimethylsulfoxide. Then, 3 g of sodium hydride (NaH) was evenly dispersed in 50 ml of DMSO, added to the beta-cyclodextrin solution prepared above, and then stirred at 21 ° C. Then, 14 ml of benzyl chloride was slowly dropped, and after about 6 hours, a precipitate was obtained using water. This precipitate was dissolved in acetone and then the impurities were removed and dried to yield a product containing Bn-β-CD. Purification with more pure results was repeated by dissolution and precipitation with acetone and methanol.

 The Bn-β-CD product obtained through this process was subjected to elemental analysis on carbon, hydrogen, and oxygen atoms to obtain the weight ratio of each element, and the results are shown in Table 1 below.

On the basis of this result, how much hydrogen of the terminal hydroxy functional group of the beta-cyclodextrin was substituted, it can be seen that 19, 90.5% of the total 21 hydroxy functional groups of the beta-cyclodextrin was replaced by the reaction with benzyl chloride there was.

element carbon Hydrogen Oxygen weight% 72.1917 6.3808 19.2859

Synthesis Example 2

This synthesis example is intended to illustrate the synthesis of the cyclodextrin derivative represented by the following formula (9) by reacting beta-cyclodextrin with 3-trimethoxysilylpropyl methacrylate represented by the formula (8).

The synthesis process of the cyclodextrin derivative of Formula 9 described above is as follows.

Prior to the modification of beta-cyclodextrin, beta-cyclodextrin was completely removed with a Dean-Stark apparatus. A reflux tube and a nitrogen inlet tube were installed in a three-necked flask, 250 ml of N, N-dimethylformamide was added thereto, and 15 g of beta-cyclodextrin was added thereto, followed by stirring to dissolve. Then, after making a vacuum in a three-necked flask, nitrogen was added and 15 ml of 3-trimethoxysilylpropyl methacrylate was added, followed by reaction for 48 hours while maintaining the temperature at 80 to 100 ° C. Then dimethylformamide was removed from the reaction solution through the column, a precipitate was obtained using acetone and then dried under vacuum for one day.

Example

This example illustrates a method for producing a plasticizer effluent reduced soft PVC composition using the cyclodextrin derivative prepared in Synthesis Example 1.

As the PVC, commercial PVC (LG Chem, LP170) was used, and as a plasticizer, dioctyl phthalate (hereinafter referred to as DOP), which is a typical low molecular weight plasticizer, was used. Epoxidized soybean oil used as a secondary plasticizer used SDB CIZER-E03 from Shindongbang, and MT-800 product from Songwon Industries.

First, the cyclotextine derivatives obtained in PVC, DOP and Synthesis Example 1, and secondary plasticizers and heat stabilizers as other additives were placed in a container according to the composition shown in Table 2 below, and mechanically stirred for 24 hours to form a plastisol. It was. The units in Table 2 are parts by weight.

number PVC DOP Secondary plasticizer Heat stabilizer Cyclodextrin derivatives system Comparative Example 1 PVC-0 100.00 57.00 3.00 2.00 - 162.00 Example 1 PVC-1 100.00 57.00 3.00 2.00 1.63 163.63 Example 2 PVC-3 100.00 57.00 3.00 2.00 5.01 167.01 Example 3 PVC-6 100.00 57.00 3.00 2.00 10.34 172.34 Example 4 PVC-9 100.00 57.00 3.00 2.00 16.02 178.02

      After forming the formed plastisol in a vacuum oven for about 2 weeks, put a certain amount in a mold and put it into the processing oven and heat it at a temperature of 180 ° C. for about 5-10 minutes to make a solution state, and then leave it at room temperature to reduce plasticizer outflow. Soft PVC samples were prepared.

Numbers of the prepared samples were selected according to the content when the content of the cyclodextrin derivatives relative to the total content of the plastisol is expressed in weight%. For example, the contents of the cyclodextrin derivatives are 0, 1, 3, 6 and 9% by weight, respectively, and the soft PVC samples generated from the plastisols are PVC-0, PVC-1, PVC-3 and PVC-6, respectively. And PVC-9.

Evaluation of Dispersion State of Cyclodextrin Derivatives

4 and 5 are photographs taken of the surface of the sample of Comparative Example 1 (PVC-0) that does not contain a cyclodextrin derivative, and the sample (PVC-9) of Example 4 that contains a predetermined amount of a cyclodextrin derivative. . 6 is a photograph of the surface of a sample prepared by dispersing pure beta-cyclodextrin in DMAc solvent.

As shown in FIG. 6, it was examined whether the flocculation phenomenon indicated as a limitation of the plasticizer effluent reduction soft PVC production method using pure beta-cyclodextrin also appeared in the soft PVC using the cyclodextrin derivative according to the present invention. As shown in the photograph, it can be seen that the surface morphology of PVC-9 is almost no difference from PVC-0, indicating that the cyclodextrin derivatives are evenly dispersed without aggregation.

Plasticizer Outflow Assessment

For the manufactured soft PVC samples, the plasticizer leakage test was carried out through the following process. The runoff experiment was based on what was specified in ISO (International Standard Organization) 3826 "Plastics collapsible containers for human blood and blood components".

First, a standard solution of various concentrations of DOP was prepared through the following process for determining the concentration of DOP, and a calibration curve preparation experiment was performed by measuring absorbance at 272 nm using an ultraviolet-visible spectrometer.

The DOP standard solution was prepared to include 1, 2, 5, 10, and 20 mg of DOP, respectively, for 100 ml of the ethyl alcohol / water mixture used in the DOP runoff experiment. Detailed preparation methods are as follows.

The ethyl alcohol / water mixed solution was mixed with ethyl alcohol and water so as to have a density of 0.9373 to 0.9378 g / ml to prepare a DOP effluent solution. In this case, the ethyl alcohol used had a purity in the range of 95.1 to 96.6% (v / v) and a density of 0.8050 to 0.8123 g / ml. 1 g of DOP was added to ethyl alcohol to a volume of 100 ml, and then 10 ml of this solution was diluted again with the effluent solution to a total volume of 100 ml. The diluted solution was taken 1, 2, 5, 10 and 20 ml, respectively, and diluted once more with the effluent solution to 100 ml. In this way, standard solutions with DOP concentrations of 1, 2, 5, 10 and 20 mg / 100 ml were prepared, respectively.

The absorbance in the 272 nm region was determined using the UV-visible spectrometer with the standard solution thus prepared, and a calibration curve as shown in FIG. 7 was prepared therefrom. The calibration curve was shown well according to Beer-Lambert's equation, and the concentration was determined by the absorbance of the sample material. The Beer-Lambert equation is expressed as Equation 2 below.

Absorbance = log (intensity of light entering the sample / intensity of light from the sample)

       = Molar extinction coefficient X concentration X length of light transmission

 The soft PVC samples prepared above were put into 100 g of the spill test solution and sealed, and the ambient temperature was maintained at 37 ± 1 ° C. The absorbance of the effluent solution at 272 nm was determined by UV-vis spectrophotometer every given time, and the absorbance was substituted into the calibration curve prepared in advance to determine the concentration of DOP from the specimens. The results are shown in Table 3 below. And this is illustrated in FIG. 8. The unit of Table 3 below is mg / 100ml.

number 6 hours later 12 hours later 24 hours later 48 hours later After 72 hours PVC-0 4.393 7.916 12.490 17.814 18.028 PVC-1 3.568 7.156 11.023 14.652 15.361 PVC-3 2.439 5.131 9.402 12.116 13.349 PVC-6 2.360 4.782 8.063 11.512 12.519 PVC-9 1.819 3.760 6.758 9.945 11.244

Referring to Table 3 and the results of FIG. 8, it is shown that the concentration of the DOP distilled decreases as the content of the cyclodextrin derivative increases, that is, from PVC-0 to PVC-9. This demonstrates that cyclodextrin derivatives reduce the outflow of DOP, a plasticizer. In particular, even if a small amount of cyclodextrin derivatives are mixed, the reduction efficiency of plasticizer outflow is greatly improved. This is because the cyclodextrin derivatives attract liquid low-molecular plasticizers into the cavity and hydrogen bonds to the outside. It is presumed that this is due to the induction of liquid low molecular plasticizers and immobilization thereof.

Properties Evaluation of Soft PVC

This evaluation is to investigate the effect of the contained cyclodextrin derivatives on the mechanical properties of soft PVC.

First, for tensile testing on the manufactured soft PVC, a dumbbell-type specimen was manufactured using a specimen maker, and a crosshead speed of 50 mm / min was used by using a universal testing machine (UTM) of Lloyd's instrument name LR10K. The load was measured by tensioning. The stresses and strains at break are shown in Table 4, and the resulting stress-strain curves are shown in FIG.

number Stress (N / mm ² ) % Strain PVC-0 21.05 445.17 PVC-1 20.29 436.65 PVC-3 20.01 433.81 PVC-6 19.83 440.78 PVC-9 17.44 418.40

Referring to Table 4 and FIG. 9, as the concentration of the cyclodextrin derivative Bn-β-CD increases, the stress and strain at the break point decrease slightly, but only a very small change within 10% is shown. have. From this, it can be confirmed that there is almost no loss of mechanical properties of the soft PVC to which the cyclodextrin derivative is added.

As described above, using a cyclodextrin derivative substituted with a predetermined compound as a compound to form a complex with the liquid low-molecular plasticizers used in the soft PVC according to the production method of the present invention, it is simple without using a solvent Economically, it is possible to mass-produce plasticizer spill-reducing soft PVC.

In addition, the prepared soft PVC is a liquid low molecular plasticizer and cyclodextrin derivatives are uniformly mixed, the cyclodextrin derivatives effectively form a complex with DOP, improving the efficiency of reducing plasticizer outflow, mechanical properties are also almost reduced Will not be.

Claims (12)

(S1) preparing a cyclodextrin derivative represented by Formula 3 below; (S2) mixing the cyclodextrin derivative, PVC and a low molecular weight plasticizer in a liquid to form a plastisol; And (S3) A method for producing a plasticizer effluent reduction soft PVC composition comprising heating the formed plastisol to a solution state and then cooling the formed plastisol. [Formula 3]

In Chemical Formula 3, R is each independently selected from hydrogen, a hydrocarbon functional group having 1 to 20 carbon atoms represented by the following Chemical Formula 4, and a silane functional group having 1 to 60 carbon atoms represented by the following Chemical Formula 5, The degree of substitution of R is 5 to 100% and n is an integer of 6 to 26. [Formula 4]

In Formula 4, a, b, c, d and e are each an integer of 0 or more, and a + b + c + d + e is 1 or more, and a combination of each structural unit according to a, b, c, d and e The order of may be randomly modified. [Formula 5]

In Formula 5, R ₁ , R ₂ , and R ₃ are each independently a hydrocarbon functional group having 1 to 20 carbon atoms represented by Formula 4. The method of claim 1, wherein the content of the cyclodextrin derivative is 2 to 20 moles based on 100 moles of the low molecular weight plasticizer in the liquid phase. The method of claim 1, wherein the low molecular weight plasticizer is a plasticizer spill reduction type soft PVC composition, characterized in that any one selected from the group consisting of phthalate plasticizer, aliphatic diester plasticizer, trimellitate plasticizer and phosphate plasticizer. Manufacturing method. The phthalate plasticizer according to claim 3, wherein the phthalate-based plasticizer is dimethyl phthalate (DMP), dibutyl phthalate (DBP), di-isobutyl phthalate (DIBP), dihexyl phthalate , DHP), dioctyl phthalate (DOP), di-iso-octyl phthalate (DIOP), dinonyl phthalate (DNP), di-isodecyl phthalate (DIDP) ), Benzyl butyl phthalate (BBP) and a method for producing a plasticizer outflow-type soft PVC composition, characterized in that any one selected from the group consisting of. According to claim 1, wherein the functional group represented by the formula (4)

Is a functional group represented by the formula (5)

Process for producing a plasticizer outflow reduced soft PVC composition, characterized in that. In a soft PVC composition comprising a PVC and a liquid low molecular plasticizer, The soft PVC composition is a plasticizer spill reduction type soft PVC composition further comprises a cyclodextrin derivative represented by the following formula (3): [Formula 3]

In Chemical Formula 3, R is each independently selected from hydrogen, a hydrocarbon functional group having 1 to 20 carbon atoms represented by the following Chemical Formula 4, and a silane functional group having 1 to 60 carbon atoms represented by the following Chemical Formula 5, The degree of substitution of R is 5 to 100% and n is an integer of 6 to 26. [Formula 4]

In Formula 4, a, b, c, d and e are each an integer of 0 or more, and a + b + c + d + e is 1 or more, and a combination of each structural unit according to a, b, c, d and e The order of may be randomly modified. [Formula 5]

In Formula 5, R ₁ , R ₂ , and R ₃ are each independently a hydrocarbon functional group having 1 to 20 carbon atoms represented by Formula 4. The method of claim 6, wherein the content of the cyclodextrin derivative is a plasticizer spill reduction type soft PVC composition, characterized in that 2 to 20 mol based on 100 mol of the low molecular weight plasticizer content of the liquid. The plasticizer spill reduction type soft PVC composition according to claim 6, wherein the liquid low molecular weight plasticizer is any one selected from the group consisting of a phthalate plasticizer, an aliphatic diester plasticizer, a trimellitate plasticizer, and a phosphate plasticizer. . According to claim 8, The phthalate plasticizer is dimethyl phthalate (dimethyl phthalate (DMP), dibutyl phthalate (DBP), di-isobutyl phthalate (DIBP), dihexyl phthalate , DHP), dioctyl phthalate (DOP), di-iso-octyl phthalate (DIOP), dinonyl phthalate (DNP), di-isodecyl phthalate (DIDP) ), Benzyl butyl phthalate (BBP) and any one selected from the group consisting of a mixture of the plasticizer outflow reduced soft PVC composition. According to claim 6, wherein the functional group represented by the formula (4)

Is a functional group represented by the formula (5)

Plasticizer spill reduction type soft PVC composition, characterized in that the. A plasticizer composition comprising a liquid low molecular plasticizer and a cyclodextrin derivative represented by Formula 3 below: [Formula 3]

In Chemical Formula 3, R is each independently selected from hydrogen, a hydrocarbon functional group having 1 to 20 carbon atoms represented by the following Chemical Formula 4, and a silane functional group having 1 to 60 carbon atoms represented by the following Chemical Formula 5, The degree of substitution of R is 5 to 100% and n is an integer of 6 to 26. [Formula 4]

In Formula 4, a, b, c, d and e are each an integer of 0 or more, and a + b + c + d + e is 1 or more, and a combination of each structural unit according to a, b, c, d and e The order of may be randomly modified. [Formula 5]

In Formula 5, R ₁ , R ₂ , and R ₃ are each independently a hydrocarbon functional group having 1 to 20 carbon atoms represented by Formula 4. The plasticizer composition according to claim 11, wherein the cyclodextrin derivative is contained in an amount of 2 to 20 moles based on 100 moles of the low molecular weight plasticizer in the liquid phase.

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