KR102135408B1 - Resin composition having migration-resistant property and the resin molded article using the same - Google Patents

Abstract

The present invention provides a resin composition comprising a resin, a plasticizer, and an alkyl acrylate oligomer and a resin molded article prepared therefrom. The resin composition provided by the present invention has an effect of improving heat resistance as well as heat resistance while maintaining excellent properties such as transparency, hardness, elongation, and fluidity. Therefore, the resin composition provided by the present invention may be useful as various molding materials such as films, tubes, pipes, cable insulation, artificial leather, wallpaper, gloves, toys, and medical containers.

Description

Resin composition with improved migration resistance and resin molded article manufactured therefrom {RESIN COMPOSITION HAVING MIGRATION-RESISTANT PROPERTY AND THE RESIN MOLDED ARTICLE USING THE SAME}

The present invention relates to the field of resin compositions. Specifically, the present invention includes resins, plasticizers, and alkyl acrylate oligomers, thereby maintaining excellent physical properties such as transparency, hardness, elongation, and fluidity, while improving heat resistance as well as migration resistance, and resin compositions prepared therefrom. It relates to a resin molded article.

A plasticizer is a material added to improve the processability by lowering the melting temperature or melt viscosity of the resin, and to provide flexibility. However, even though the plasticizer is a useful additive for improving the flexibility and the like of the resin, since it has insufficient compatibility with the resin, there is a disadvantage in that it is easily converted to the outside due to the surrounding environment or chemical or physical contact. Such a plasticizer is more serious in a monomolecular plasticizer having a lower molecular weight than a plasticizer having a high molecular weight. When the plasticizer is easily transferred from the resin to the outside, the plasticizing effect of the resin is improved even if an excess plasticizer is added. Unexpectedly, plasticizers released to the outside cause serious environmental problems such as acting as environmental hormones harmful to the human body. In view of the fact that the plasticizer contains an excess of 50 parts by weight or more of a plasticizer based on 100 parts by weight of the resin, the performance problem of the plasticizer is an essential problem to be solved.

Korean Patent Publication No. 10-2017-0066668

The technical problem to be solved by the present invention is to provide a resin composition containing a resin and a plasticizer, the resin having an improved migration resistance, which can suppress the external release of the plasticizer while maintaining or improving the favorable physical properties of the resin. It is an object to provide a composition.

In addition, another technical problem to be solved by the present invention is to provide a resin molded article with improved migration resistance that suppresses plasticizer release to the outside.

According to one aspect of the present invention for solving the above problems, it is possible to provide a resin composition having improved migration resistance. According to one embodiment, the resin composition having improved migration resistance is a resin; Plasticizers; And an alkyl acrylate oligomer having a number average molecular weight of 500 to 5,000 g/mol; It may include.

According to one embodiment, in the resin composition having improved migration resistance, the resin is polyethylene (PE), polypropylene (PP), polystyrene (PS), polyamide (PA), and polyvinyl chloride (PVC). It may include one or two or more thermoplastic resins selected from the group consisting of. According to a specific embodiment, the resin may include polyvinyl chloride (PVC).

According to one embodiment, in the resin composition having improved migration resistance, the plasticizer may include an ester plasticizer obtained by reacting a polycarboxylic acid compound with a linear or branched aliphatic alcohol compound having 3 to 15 carbon atoms. have. According to a specific embodiment, the plasticizer is dibutyl phthalate (DBP), di(2-ethylhexyl) phthalate (DEHP), dioctyl phthalate (DOP), di(isononyl) phthalate (DINP), di(2-propyl) Phthalate plasticizers selected from the group consisting of heptyl) phthalate (DPHP) and di(isodecyl) phthalate (DIDP); An adipate-based plasticizer selected from the group consisting of dioctyl adipate (DOA) and di(isononyl) adipate (DINA); And a trimellitate plasticizer selected from the group consisting of tri(2-ethylhexyl) trimellitate, trioctyl trimellitate and trimdecyl trimellitate; It may include one or two or more selected from the group consisting of. In addition, a cyclohexane-based plasticizer may be included. According to a more specific embodiment, the plasticizer may include a phthalate-based plasticizer.

According to one embodiment, in the resin composition having improved migration resistance, the alkyl acrylate oligomer acts as a compatibilizer to improve the compatibility between the resin and the plasticizer, thereby acting as a migration inhibitor of the plasticizer. have. According to a specific embodiment, the alkyl acrylate oligomer is a polymer of alkyl acrylate monomers in which an alkyl group having 1 to 15 carbon atoms is bonded, and the number average molecular weight may be 500 to 5,000 g/mol. According to a more specific embodiment, the alkyl acrylate oligomer may be a butyl acrylate oligomer having a number average molecular weight of 1,000 to 3,000 g/mol.

According to one embodiment, in the above-described resin composition having improved migration resistance, an additive selected from the group consisting of a stabilizer, a filler, and the like may be further included.

According to one embodiment, in the resin composition having improved migration resistance, the plasticizer may include 30 to 50 parts by weight of the plasticizer and 0.1 to 20 parts by weight of the alkyl acrylate oligomer.

According to another aspect of the present invention, it is possible to provide a resin molded article with improved migration resistance. According to one embodiment, the resin molded article with improved migration resistance may be molded using a resin composition as a material. According to a specific embodiment, the molded article may be selected from the group consisting of film, tube, pipe, cable insulation, artificial leather, wallpaper, gloves, toys and medical containers. According to a more specific embodiment, the molded article may be a medical tube for injecting an injection solution.

According to an embodiment of the present invention, when an alkyl acrylate oligomer having a predetermined molecular weight is included in a resin composition containing a conventional resin and a conventional plasticizer, the effect of solving the problem of migration, which is the greatest disadvantage of the plasticizer, is exceptional. Do. Particularly, the above-described alkyl acrylate oligomer is included in a composition containing a phthalate plasticizer widely used in the art, so the effect of suppressing the migration of a phthalate plasticizer is very special.

According to an embodiment of the present invention, since the alkyl acrylate oligomer is excellent in compatibility with each of a common resin or a conventional plasticizer, the alkyl acrylate oligomer serves as a compatibilizer to improve the compatibility between the resin and the plasticizer Can be expected. Therefore, when an alkyl acrylate oligomer having a predetermined molecular weight is included in a resin composition containing a conventional resin and a conventional plasticizer, the effect of improving the plastic agent's migration resistance while maintaining or improving the natural properties of the resin can be expected. have.

According to an embodiment of the present invention, a resin composition containing a resin, a plasticizer, and an alkyl acrylate oligomer having a predetermined molecular weight, while maintaining excellent properties such as transparency, hardness, elongation, and fluidity of the resin, heat resistance and transfer resistance Can improve the effect at the same time.

According to an embodiment of the present invention, the resin composition provided by the present invention may be useful as a molding material for molded products selected from the group consisting of films, tubes, pipes, cable insulation, artificial leather, wallpaper, gloves, toys, and medical containers. have.

1 is a diagram of GPC analysis for the butyl acrylate oligomer (pBA) obtained in Synthesis Examples 1-3.
Figure 2 is a FT-IR spectrum for the butyl acrylate oligomer (pBA) obtained in Synthesis Examples 1-3.
3 is a ¹ H-NMR spectrum for the butyl acrylate oligomer (pBA1000) obtained in Synthesis Example 1.
4 is a ¹ H-NMR spectrum for the butyl acrylate oligomer (pBA1800) obtained in Synthesis Example 2.
5 is a ¹ H-NMR spectrum for the butyl acrylate oligomer (pBA2500) obtained in Synthesis Example 3.
6 is a graph showing the results of evaluating the transmittance of the PVC film to which the butyl acrylate oligomer is added.
7 is a graph showing the results of dynamic dynamic analysis (DMA) for a PVC film to which butyl acrylate oligomer is added.
8 is a graph showing the results of evaluating thermal properties using a thermogravimetric analyzer (TGA) for a PVC film to which butyl acrylate oligomer is added.
9 is a graph showing the results of measuring Shore A hardness to evaluate the degree of plasticity for a PVC specimen to which a butyl acrylate oligomer is added.
10 is a graph showing the results of measuring the elongation with respect to the PVC specimen to which the butyl acrylate oligomer is added.
11 is a graph showing the results of evaluating migration resistance (70°C deionized water solvent system) for a PVC specimen to which a butyl acrylate oligomer is added.
12 is a graph showing the results of evaluating migration resistance (25° C. ethanol aqueous solvent system) for a PVC specimen to which butyl acrylate oligomer is added.

Hereinafter, the present invention will be described in more detail based on the following examples, but the following examples are only for illustrating the present invention, and the scope of the present invention is not limited thereby.

The embodiments of the present invention are provided to more fully describe the present invention to those of ordinary skill in the art, and the following examples may be modified in various other forms, and the scope of the present invention is as follows. It is not limited to the Examples. Rather, these examples are provided to make the present disclosure more faithful and complete, and to fully convey the spirit of the present invention to those skilled in the art.

In addition, the term "aliphatic" as used herein refers to a compound belonging to an organic class in which atoms are not linked together to form an aromatic ring. As one of the major structural groups of organic molecules, the aliphatic compounds include alkanes comprising substances derived from linear, branched, cyclic, and those in which one or more hydrogen atoms are actually or theoretically substituted by other elements or groups of atoms. , Alkenes, and alkynes.

In addition, the term "aromatic" as used herein refers to a compound that is one of a large class of unsaturated chemical compounds characterized by one or more planar rings joined by covalent bonds, some of which are alternating single or double bonds. And the characteristic properties of these compounds are aromatic. The directionality results from a specific binding arrangement that allows the π(pi) electrons to be contained in a strongly open molecule. Benzene, toluene, and naphthalene are the most well-known aromatic compounds and constitute the matrix of other aromatic compounds.

In addition, the terms used in this specification are used to describe the embodiments, and are not intended to limit the scope of the present invention. In addition, even if it is described in the singular in this specification, unless the context clearly indicates the singular, it may include a plurality of forms. Also, as used herein, the terms “comprise” and/or “comprising” specify the shapes, numbers, steps, actions, elements, elements and/or the presence of these groups. Does not exclude the presence or addition of other shapes, numbers, actions, elements, elements and/or groups.

In addition, the term “parts by weight (phr)” used in this specification is a unit indicating the content of the resin composition, and indicates the weight of each component included based on 100 parts by weight of the resin. In preparing the resin composition of the present embodiment, 100 parts by weight of the resin is used, and 50 parts by weight of the DEHP plasticizer is used based on 100 parts by weight of the resin, and the alkyl acrylate oligomer may be prepared by using 5 parts by weight or 10 parts by weight.

The present invention will be described in more detail as follows.

The present invention is a resin composition comprising a conventional resin and a conventional plasticizer, the plasticizer is leached from the resin and released to the outside, so as to solve the problem of'migration property', and is required for the resin composition The present invention relates to a resin composition that simultaneously improves mechanical properties and thermal stability, and a resin molded article produced therefrom.

According to an embodiment of the present invention, a resin composition with improved performance can be provided.

The resin composition provided by the present invention may include a resin, a plasticizer, and an alkyl acrylate oligomer having a number average molecular weight of 500 to 5,000 g/mol. Specifically, the resin composition of the present invention may include 100 parts by weight of a resin, 30 to 80 parts by weight of a plasticizer, and 0.1 to 20 parts by weight of an alkyl acrylate oligomer.

The resin contained in the resin composition of the present invention is specifically, one or two selected from the group consisting of polyethylene (PE), polypropylene (PP), polystyrene (PS), polyamide (PA) and polyvinyl chloride (PVC). More than one type of thermoplastic resin can be used universally.

More specifically, the resin may be polyvinyl chloride (PVC). The polyvinyl chloride (PVC) may be a homopolymer, a copolymer, polyvinyl dichloride (PVDC), or a similar polymer thereof. Further, the polyvinyl chloride (PVC) may be suspended PVC, bulk PVC, microsuspension PVC or emulsion PVC based on the polymerization method.

The plasticizer included in the resin composition of the present invention can be used universally as an ester plasticizer. The ester plasticizer can be obtained through an esterification reaction of a polycarboxylic acid compound and an alcohol compound. The polycarboxylic acid compound is an aliphatic or aromatic compound containing two or more carboxylic acid groups, and specifically, adipic acid, phthalic acid, trimellitic acid, and the like may be included. The alcohol compound is an alcohol having 3 to 15 carbon atoms, specifically, propanol, butanol, hexanol, octanol, 2-ethylhexanol, 3-ethylhexanol, 2-propylheptanol, isononyl alcohol, and isodecyl Alcohol, and the like.

Specifically, the ester plasticizer may be one or two or more selected from the group consisting of adipate plasticizers such as dioctyl adipate (DOA) and di(isononyl) adipate (DINA). In addition, the ester plasticizer is specifically, dibutyl phthalate (DBP), di(2-ethylhexyl) phthalate (DEHP), dioctyl phthalate (DOP), di(isononyl) phthalate (DINP), di(2- Propylheptyl) phthalate (DPHP) or di(isodecyl) phthalate (DIDP). In addition, the ester plasticizer is specifically, one or two or more selected from the group consisting of trimellitate plasticizers such as tri(2-ethylhexyl) trimellitate, trioctyl trimellitate, trimdecyl trimellitate. Can.

Further, the ester plasticizer may be one or two or more selected from the group consisting of the above-mentioned adipate plasticizer, phthalate plasticizer, and trimellitate plasticizer. In addition, a cyclohexane-based plasticizer may be included.

The plasticizer may be included in the range of 30 to 80 parts by weight, more specifically 30 to 50 parts by weight based on 100 parts by weight of the resin constituting the resin composition. In the case of a conventional plasticized resin composition, the plasticizer contains an excess of 50 parts by weight, based on 100 parts by weight of the resin, due to the problem that the plasticizer is easily transferred from the resin to the outside. However, in the present invention, it is possible to use a small amount of the plasticizer content of 50 parts by weight or less based on 100 parts by weight of the resin by improving the migration resistance of the plasticizer. That is, according to the present invention, even if a small amount of a plasticizer is contained in the resin composition, there is an advantage that a sufficient plasticizing effect can be expected.

The alkyl acrylate oligomer included in the resin composition of the present invention acts as a compatibilizer that improves the compatibility between the resin and the plasticizer, and thus can act as a migration inhibitor of the plasticizer. In addition, the alkyl acrylate oligomer has a solubility parameter of 16 to 20. The alkyl acrylate oligomer solubility coefficient has an approximate value compared to the theoretical solubility coefficient of a conventional resin or plasticizer, and thus, it is judged that compatibility with these resins or plasticizers is excellent. The transfer resistance of the alkyl acrylate oligomer is very effective when it is included in a resin composition containing a phthalate plasticizer widely used in the art.

The alkyl acrylate oligomer may be a polymer of an alkyl acrylate monomer in which an alkyl group having 1 to 15 carbon atoms is bonded, and the alkyl acrylate oligomer may have a number average molecular weight of 500 to 5,000 g/mol. Specifically, the alkyl acrylate oligomer may be a butyl acrylate oligomer having a number average molecular weight of 1,000 to 3000 g/mol.

More specifically, the alkyl acrylate oligomer may be represented by the following Chemical Formula 1 or Chemical Formula 2.

(In Formula 1, n is an integer of 4 to 40, R ¹ is an alkyl group having 1 to 15 carbon atoms)

(In Formula 2, n is an integer of 4 to 40, R ¹ , R ² and R ³ are the same or different from each other, and are alkyl groups having 1 to 15 carbon atoms)

The alkyl acrylate oligomer may be included in the range of 0.1 to 20 parts by weight, more specifically 5 to 15 parts by weight based on 100 parts by weight of the resin constituting the resin composition. If the content of the alkyl acrylate oligomer is less than 0.1 part by weight, the effect of its addition cannot be expected. In addition, the content of the alkyl acrylate oligomer exceeds 20 parts by weight, and may be a factor that degrades the physical properties of the resin composition or the resin molded article.

The resin composition of the present invention may further include additives selected from the group consisting of stabilizers, fillers, and the like. The selection and content of these additives can be appropriately adjusted within the range permitted in the art, and the present invention is not particularly limited with respect to the selection and content of these additives.

The stabilizer may be added to prevent deterioration of the resin and/or plasticizer due to heat, light or oxygen in the air under the use environment. The stabilizer is a metal-based stabilizer lead sulfate; Stearic acid salts such as lead stearate, cadmium stearate, magnesium stearate, calcium stearate, zinc stearate, barium stearate, and complex stearic acid salts of calcium and zinc; Tin compounds such as dibutyl tin laurate and dibutyl tin sulfonate; Carbonates such as aluminum carbonate, magnesium carbonate, and complex carbonates of aluminum and magnesium; Phenolic compounds; Phosphoric acid ester-based compounds; Or phosphorous acid ester-based compounds; One or two or more selected from the group consisting of the like may be included. The stabilizer can be appropriately selected according to the application. The stabilizer may be included in a range of less than 10 parts by weight, more specifically 1 to 5 parts by weight based on 100 parts by weight of the resin constituting the resin composition. When the content of the stabilizer exceeds 10 parts by weight, an excessive amount of heat stability may be exhibited.

Specifically, the filler may include one or two or more selected from the group consisting of calcium carbonate, diatomaceous earth, clay, and talc. In addition, the filler may include naturally occurring silicate or natural carbonate. The filler may be included in a range of less than 50 parts by weight, more specifically 10 to 30 parts by weight based on 100 parts by weight of the resin constituting the resin composition. When the content of the filler exceeds 50 parts by weight, an excessive amount may be included, which may be a factor that deteriorates tensile strength, elongation, and workability.

According to another embodiment of the present invention, it is possible to provide a resin molded article with improved migration resistance manufactured using the above-described resin composition.

The resin composition has excellent properties such as transparency, hardness, elongation, and fluidity while maintaining excellent properties, while improving heat resistance and transfer resistance. Accordingly, the resin composition may be useful as a molding material for molding into films, tubes, pipes, cable insulation, artificial leather, wallpaper, gloves, toys, and medical containers. In particular, the resin composition has excellent properties of migration resistance, and thus can be preferably used as a molding material for molding a medical tube for injecting an injection solution.

The method for manufacturing a resin molded article using the resin composition may be carried out by a conventional molding method, and such molding method may be applied to a method widely used in the art. The present invention is not limited to a method for producing a resin molded article using the resin composition.

Hereinafter, preferred examples are provided to help understanding of the present invention, but the following examples are merely illustrative of the present invention and the scope of the present invention is not limited to the following examples. It is obvious to those skilled in the art that various modifications and variations are possible within the technical scope of the present invention, and it is natural that such modifications and modifications belong to the appended claims.

[Example]

Synthetic example. Synthesis of alkyl acrylate oligomer

The alkyl acrylate oligomer was synthesized by GTP polymerization (Group transfer polymerization) or radical polymerization (Radical polymerization).

Synthesis Example 1. Synthesis of butyl acrylate oligomer having a number average molecular weight of 1,000 g/mol

A butyl acrylate oligomer having a number average molecular weight of 1000 g/mol was synthesized using GTP polymerization (Group transfer polymerization). The specific synthesis method is as described below.

The dropping funnel and the temperature sensor of the thermal stirrer were connected to the flask and purged with nitrogen. Into the flask, 0.04 g of tetrabutylammonium 3-chlorobenzoate (TBACB) catalyst, 1.74 g of methyl trimethylsilyl dimethylketene acetal, 2.49 g of THF, and 0.4 g of acetonitrile as a GTP initiator were added, followed by stirring at 700 rpm at room temperature. Stir at speed for 30 minutes. After 30 minutes, 5 g of butyl acrylate monomer was placed in the dropping funnel, and then charged over about 1 hour. The reaction was carried out for 5 hours at 700 rpm stirring speed at room temperature. During the reaction, the molecular weight and dispersion degree (PDI) of the oligomer produced by gel permeation chromatography (GPC) were monitored, and after confirming that it was close to the target molecular weight, methanol was added to terminate the polymerization reaction. After completion of the polymerization reaction, washing was performed with a 50% aqueous ethanol solution, followed by drying to obtain an oligomer product (conversion rate: 95% or higher, yield: 90%).

Synthesis Examples 2 and 3. Synthesis of butyl acrylate oligomer having a number average molecular weight of 1,800 or 2,500 g/mol

Butyl acrylate oligomers having a number average molecular weight of 1,800 g/mol and 2,500 g/mol were synthesized by using radical polymerization. The specific synthesis method is as described below.

After connecting the reflux cooler and the temperature sensor of the heat stirrer to the three-necked flask, 30 g of butyl acrylate monomer and 0.66 g of 2,2-azobis(2-methylpropionitrile) (AIBN) as a radical initiator were added and chained. As the transfer agent, dodetanthiol 3.4 g (target molecular weight 1,800 g/mol) or 2.44 g (target molecular weight 2,500 g/mol) were added, respectively. Thereafter, the toluene reaction solvent was added at a weight ratio of 30%. The polymerization reaction was carried out while the reaction mixture was stirred at a temperature of 115°C at a stirring speed of 800 rpm. During the reaction, the molecular weight and dispersion degree (PDI) of the oligomer produced by gel permeation chromatography (GPC) were monitored, and after confirming that it was close to the target molecular weight, air was injected to terminate the polymerization reaction. The reactant having a target number average molecular weight of 1,800 g/mol was washed with a 50% aqueous ethanol solution, and the reactant having a target number average molecular weight of 2,500 g/mol was washed with a solvent fractionation method based on normal hexane. After washing, it was dried to obtain an oligomer product (conversion rate: 80%, yield: 65%).

The molecular weight and dispersion degree (PDI) of each of the butyl acrylate oligomers (pBA) obtained in Synthesis Examples 1 to 3 were measured and summarized in Table 1 below, and the results of GPC analysis were attached to FIG. 1.

division Mark Mn Mw PDI (Mw/Mn) Synthesis Example 1 pBA1000 1,011 1,451 1.436 Synthesis Example 2 pBA1800 1,759 3,257 1.852 Synthesis Example 3 pBA2500 2,509 4,585 1.827

According to Table 1, it can be seen that the butyl acrylate oligomers (pBA) obtained in Synthesis Examples 1 to 3 have a narrow molecular weight distribution with a PDI of less than 2.

In addition, FT-IR spectrum for each of the butyl acrylate oligomers (pBA) obtained in Synthesis Examples 1 to 3 was attached to FIG. 2. According to FIG. 2, it was confirmed that the peak of the C=C stretch characteristic of the acrylic monomer identified at 1540 to 1650 cm ⁻¹ disappeared. In addition, as an acrylate characteristic peak, an alkyl CH stretch characteristic peak in a region of 3000 cm ^-1 or more and a C=O stretch characteristic peak in 1650 to 1800 cm ^-1 were confirmed. Therefore, it can be seen that butyl acrylate oligomer (pBA) was synthesized through Synthesis Examples 1-3.

In addition, ¹ H-NMR spectrum for each of the butyl acrylate oligomers (pBA) obtained in Synthesis Examples 1 to 3 was attached to FIGS. 3 to 5.

3 is a spectrum of pBA1000 synthesized by GTP polymerization by Synthesis Example 1. According to FIG. 3, Ha of the butyl group terminal was characteristically found at 0.9 ppm, Hh next to the ester functional group was 4.0 ppm, and Hc, Hd, He, and Hf of the polymer chain of the second and third alkyl groups of the butyl group were 1.2. To 2.5 ppm. And, Hb and Hg derived from the GTP initiator were found to be characteristically at 1.1 and 3.6 ppm, respectively.

4 and 5 are pBA1800 and pBA2500 spectra synthesized by a radical polymerization method. According to FIGS. 4 and 5, Ha at the end of the butyl group was characteristically found at 0.9 ppm, Hh next to the ester functional group was 4.0 ppm, and the alkyl chain of the second and third alkyl groups of the butyl group and chain transfer agent (CTA). The Hb, Hc, Hd, He and Hf of the main polymer backbone were characterized by 1.2 to 2.5 ppm.

As a result of analyzing the above ¹ H NMR spectrum, it can be confirmed that the desired butyl acrylate oligomer (pBA) was synthesized through Synthesis Examples 1 to 3.

Reference Example: Determination of the compatibility of alkyl acrylate oligomers to PVC or DEHP plasticizers

For each of the alkyl acrylate oligomers synthesized in Synthesis Examples 1 to 3, compatibility with polyvinyl chloride (PVC) or di(2-ethylhexyl)phthalate (DEHP) plasticizer was evaluated. Specifically, compatibility is a solubility coefficient [Reference: Solubility parameter; Eric A. Grulke, Solubility Parameter Value , University of Kentucky, USA].

Table 2 is a result of mixing polyvinyl chloride (PVC) and an alkyl acrylate oligomer in a 1:1 weight ratio, and evaluating compatibility after 24 hours.

Evaluation of the compatibility of alkyl acrylate oligomers with PVC division Theoretical Solubility Coefficient Judging compatibility with PVC PVC Alkyl acrylate
Oligomer PVC/pBA1000 19.95 17.63 Excellence PVC/pBA1800 17.11 Excellence PVC/pBA2500 16.77 Excellence

Table 3 below shows the results of mixing the di(2-ethylhexyl)phthalate (DEHP) plasticizer and the alkyl acrylate oligomer in a 1:1 weight ratio and evaluating compatibility after 24 hours.

Evaluation of the compatibility of alkyl acrylate oligomers with DEHP plasticizers division Theoretical Solubility Coefficient Determining compatibility with DEHP DEHP plasticizer Alkyl acrylate
Oligomer DEHP/pBA1000 18.51 17.63 Excellence DEHP/pBA1800 17.11 Excellence DEHP/pBA2500 16.77 Excellence

According to Tables 2 and 3, it can be seen that the alkyl acrylate oligomers synthesized in Synthesis Examples 1 to 3 have approximate theoretical solubility coefficients when compared with PVC or DEHP plasticizers. Therefore, it is determined that the alkyl acrylate oligomers synthesized in Synthesis Examples 1 to 3 have excellent compatibility with thermoplastic resins and plasticizers.

Comparative Example 1 and Examples 1 to 6: Preparation of resin composition

Resin compositions containing butyl acrylate oligomers synthesized in Synthesis Examples 1 to 3, respectively, were prepared. Table 4 below shows the composition components and composition ratios constituting the resin composition.

As the resin, polyvinyl chloride (PVC; Hanwha Chemical KL-10) was selected as the representative of the thermoplastic resin, and di(2-ethylhexyl)phthalate (DEHP; Sigma Aldrich) was selected as the phthalate plasticizer as the plasticizer. Did. As an additive, Songwon Industrial's thermal stabilizer (SONGSTAB™ BZ-119) was used. In this embodiment, PVC is used as the thermoplastic resin and DEHP is used as the plasticizer, but the embodiment of the present invention is not limited thereto.

division Content (parts by weight) PVC DEHP Heat stabilizer Alkyl acrylate oligomer Kinds content Comparative Example 1 100 50 3 - - Example 1 100 50 3 pBA1000 5 Example 2 100 50 3 pBA1000 10 Example 3 100 50 3 pBA1800 5 Example 4 100 50 3 pBA1800 10 Example 5 100 50 3 pBA2500 5 Example 6 100 50 3 pBA2500 10

[Experimental Example] In order to confirm the physical properties of the resin composition prepared in Comparative Example 1 and Examples 1 to 6, the following experiment was performed.

Experimental Example 1. Evaluation of the transmittance of the resin composition

In order to evaluate the transmittance of the resin composition prepared in Comparative Examples 1 and 1 to 6, a soft PVC film was prepared by a casting method. Specifically, the resin composition shown in Table 4 was mixed in a tetrahydrofuran (THF) solvent and stirred for 12 hours to prepare a PVC mixed solution. The prepared PVC mixed solution was poured into a partition wall (150*150*15 mm) formed on a glass substrate. After removing most of the THF solvent at room temperature, gelation was performed at 75°C for 30 minutes to prepare a transparent soft PVC film having an average thickness of 0.15 mm.

To evaluate how the introduction of the butyl acrylate oligomer affects the transmittance of the soft PVC film, the transmittance was measured using an ultraviolet-visible spectrophotometer (UV-Visible Spectrophotometer, V-770, JASCO). The results are shown in FIG. 6.

In FIG. 6, the transmittance of the films containing 10 parts by weight of butyl acrylate oligomers (pBA1000, pBA1800, and pBA2500) was compared and compared with the film of Comparative Example 1 in which butyl acrylate oligomer was not added. According to FIG. 6, it can be confirmed that introduction of butyl acrylate oligomer hardly affects the transmittance of the soft PVC film. That is, since the added butyl acrylate oligomer has excellent compatibility with PVC resin and DEHP plasticizer, it can be seen that there is no fear of lowering the transparency of the film due to the addition.

Experimental Example 2. Evaluation of the thermal properties of the resin composition

In order to evaluate the thermal properties of the resin composition prepared in Comparative Example 1 and Examples 1 to 6, a soft PVC film was prepared by the casting method illustrated in Experimental Example 1.

In order to evaluate how the introduction of butyl acrylate oligomer affects the thermal properties of soft PVC films, dynamic dynamic analysis (DMA, DMA/SS6100, Seiko Exstar) and thermogravimetric analyzer (TGA, Q50, TA Analysis) The glass transition temperature was measured using.

7 and Table 5 below show the results of measuring the glass transition temperature of the soft PVC film by dynamic mechanical analysis (DMA).

division Furtherance Glass transition temperature (℃) Comparative Example 1 PVC/DEHP
(100/50phr) 5.2 Example 2 PVC/DEHP/pBA1000
(100/50/10phr) -5.2 Example 4 PVC/DEHP/pBA1800
(100/50/10phr) -5 Example 6 PVC/DEHP/pBA2500
(100/50/10phr) -5.4

According to FIG. 7 and Table 5, compared to the film of Comparative Example 1 in which butyl acrylate oligomer was not added, films containing 10 parts by weight of butyl acrylate oligomers (pBA1000, pBA1800, pBA2500) each had a glass transition temperature ( It can be seen that Tg) is lowered by about 10°C. In addition, it was confirmed that the change in Tg according to the molecular weight change of the butyl acrylate oligomer was insignificant. These results show that the butyl acrylate oligomer itself has a plasticizing effect on PVC, and thus it is judged to significantly increase the free volume when using DEHP alone. In addition, FIGS. 8 and 6 show softness by thermogravimetric analysis (TGA). The results of monitoring the temperature of 10% by weight of the PVC film (Temperature of 10% weight loss, Td10) are shown.

division Furtherance Td10 (℃) Comparative Example 1 PVC/DEHP
(100/50phr) 219 Example 2 PVC/DEHP/pBA1000
(100/50/10phr) 232 Example 4 PVC/DEHP/pBA1800
(100/50/10phr) 231 Example 6 PVC/DEHP/pBA2500
(100/50/10phr) 232

According to FIG. 8 and Table 6, compared to the film of Comparative Example 1 in which butyl acrylate oligomer was not added, the film containing 10 parts by weight of butyl acrylate oligomer (pBA1000, pBA1800, pBA2500) each had a Td10 of about 10 It can be confirmed that the temperature has risen above ℃. These results show that the butyl acrylate oligomer is well bound in PVC through a polar bond with a DEHP plasticizer, reducing the transferability to the film surface due to heat and reducing the volatilization of subsequent DEHP.

Experimental Example 3. Shore A hardness evaluation of resin composition

In order to evaluate how the introduction of butyl acrylate oligomer affects the plasticity of the PVC composition, Shore A hardness was measured after preparing a 30*30*15 mm specimen according to ASTM D2240. The results are shown in FIG. 9.

According to Figure 9, compared to the specimen without the addition of butyl acrylate oligomer, the specimen containing 10 parts by weight of butyl acrylate oligomer (pBA1000, pBA1800, pBA2500) each has little difference in Shore A hardness difference within ± 1 can confirm. That is, since the added butyl acrylate oligomer has excellent compatibility with PVC resin and DEHP plasticizer, it can be seen that there is no fear of lowering the Shore A hardness of the PVC composition due to the addition thereof.

Experimental Example 4. Evaluation of elongation of resin composition

To evaluate the effect of the introduction of butyl acrylate oligomer on the elongation of the PVC composition, a 24.5*100*0.150 mm specimen was prepared according to ASTM D882, and then a universal tester (UTM, LR30K, LLOYD Instruments) was used. Elongation was measured. The results are shown in Figure 10.

According to Figure 10, compared to the specimen is not added butyl acrylate oligomer, it can be seen that the specimen containing 10 parts by weight of butyl acrylate oligomer (pBA1000, pBA1800, pBA2500), respectively, has little difference in elongation. That is, since the added butyl acrylate oligomer has excellent compatibility with PVC resin and DEHP plasticizer, it can be seen that there is no fear of lowering the elongation of the PVC composition due to its addition.

Experimental Example 5. Evaluation of migration resistance of resin composition

* To evaluate how the introduction of butyl acrylate oligomer affects the migration resistance of the PVC composition, a 50*50*0.150 mm specimen was prepared according to ASTM D1239. The prepared specimens were placed in 70°C deionized water for 24 hours, and then the weightability was evaluated through weight measurement. In addition, the prepared specimens were placed in a 50% aqueous ethanol solution at 25° C. for 24 hours, and then the weightability was evaluated through weight measurement. Based on the results of evaluating plasticizer performance in two solvent systems of deionized water or ethanol aqueous solution, the degree of performance was measured according to the following equation (1). The degree of migration measured in the two solvent systems is shown in FIGS. 11 and 12, respectively.

(In Equation 1 above, W represents the weight of the specimen _before impregnation, W represents the weight of the specimen _after impregnation, and A represents the weight fraction of the plasticizer in the specimen)

According to FIGS. 11 and 12, compared to the specimen to which the butyl acrylate oligomer is not added, the specimen containing 5 parts by weight or 10 parts by weight of butyl acrylate oligomers (pBA1000, pBA1800, pBA2500) respectively performs 41 to 41 parts of plasticizer. It was confirmed to reduce by 45%. In addition, it can be seen that the lower the molecular weight of the butyl acrylate oligomer, the higher the transition reduction efficiency. In the case of a butyl acrylate oligomer having a relatively higher molecular weight, it is judged that the free volume increases, and the polarization effect between the butyl acrylate and the DEHP plasticizer is partially offset, leading to more progress of the plasticizer. In addition, it was confirmed that the increase in the addition amount of the butyl acrylate oligomer does not significantly affect the performance of the DEHP plasticizer.

Claims (9)

100 parts by weight of resin;
30 to 50 parts by weight of a phthalate plasticizer; And
It is a polymer of an alkyl acrylate monomer in which an alkyl group having 1 to 15 carbon atoms is bonded, and contains 0.1 to 20 parts by weight of a butyl acrylate oligomer compatibilizer having a number average molecular weight of 1,000 to 3,000 g/mol,
The butyl acrylate oligomer compatibilizer is a resin composition with improved migration resistance that acts as a compatibilizer between the resin and the phthalate plasticizer. According to claim 1,
The resin is one or two or more thermoplastic resins selected from the group consisting of polyethylene (PE), polypropylene (PP), polystyrene (PS), polyamide (PA), and polyvinyl chloride (PVC). Resin composition. According to claim 1,
The resin is a polyvinyl chloride (PVC) resin composition with improved migration resistance. According to claim 1,
The plasticizer is an ester plasticizer obtained by reacting a polycarboxylic acid compound with a linear or branched aliphatic alcohol compound having 3 to 15 carbon atoms, and the resin composition having improved migration resistance. According to claim 1,
The phthalate-based plasticizer is dibutyl phthalate (DBP), di(2-ethylhexyl) phthalate (DEHP), dioctyl phthalate (DOP), di(isononyl) phthalate (DINP), di(2-propylheptin) phthalate ( DPHP), and di(isodenyl) phthalate (DIDP). According to claim 1,
The dispersibility (PDI) of the butyl acrylate oligomer compatibilizer is less than 2 resin composition with improved migration resistance. According to claim 1,
The butyl acrylate oligomer compatibilizer has a solubility parameter (Solubility Parameters) of 16 to 20 resin composition is improved migration resistance. According to claim 1,
The butyl acrylate oligomer compatibilizer is a resin composition having improved migration resistance represented by the following Chemical Formula 1 or Chemical Formula 2.
[Formula 1]

[Formula 2]

In Formula 1, n is an integer of 4 to 40, R ¹ is an alkyl group having 1 to 15 carbon atoms, and in Formula 2, n is an integer of 4 to 40, and R ¹ , R ² and R ³ are each other The same or different, alkyl group having 1 to 15 carbon atoms. According to claim 1,
The butyl acrylate oligomer compatibilizer is a resin composition with improved transfer resistance synthesized by GTP polymerization (Group transfer polymerization) or radical polymerization (Radical polymerization).

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