KR20190115275A - 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 produced therefrom. The resin composition provided by the present invention has improved heat resistance and migration resistance while maintaining excellent properties in terms of transparency, hardness, elongation, fluidity, etc. Accordingly, the resin composition provided by the present invention may be useful as molding material for various articles, such as films, tubes, pipes, cable insulating material, synthetic leather, wallpapers, gloves, toys, and medical containers.

Description

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 a resin, a plasticizer, and an alkyl acrylate oligomer, thereby maintaining excellent physical properties such as transparency, hardness, elongation, fluidity, and the like, and a resin composition having improved heat resistance as well as migration resistance. It relates to a resin molded article.

A plasticizer is a substance added to lower the melting temperature or melt viscosity of the resin to improve processability and to impart flexibility. However, although the plasticizer is a useful additive for improving the flexibility of the resin, etc., since the compatibility with the resin is insufficient, there is a disadvantage that the plasticizer is easily made to the outside by the surrounding environment or by chemical or physical contact. Such a plasticizer is more serious in a low molecular weight plasticizer than a plasticizer having a high molecular weight. Thus, when the plasticizer is easily transferred from the resin to the outside, even if an excess plasticizer is added, the plasticizing effect of the resin is increased. Unexpectedly, the plasticizer released to the outside causes serious environmental problems such as acting as an environmental hormone substance harmful to the human body. Considering that an ordinary plasticized resin composition contains an excessive amount of the plasticizer in an amount of 50 parts by weight or more 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, in providing a resin composition containing a resin and a plasticizer, the resin has improved migration resistance, which can suppress the external release of the plasticizer while maintaining or improving the beneficial properties of the resin intact 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 in which plasticizer release is suppressed to the outside.

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

According to one embodiment, in the resin composition with 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 with improved migration resistance, the plasticizer may include an ester plasticizer obtained by reacting a polycarboxylic acid compound and 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); Adipate-based plasticizers selected from the group consisting of dioctyl adipate (DOA) and di (isononyl) adipate (DINA); And trimellitate plasticizers selected from the group consisting of tri (2-ethylhexyl) trimellitate, trioctyl trimellitate and tridecyl 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 plasticizer.

According to one embodiment, in the resin composition with improved migration resistance, the alkyl acrylate oligomer may act 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 an alkyl acrylate monomer bonded to an alkyl group having 1 to 15 carbon atoms, 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 resin composition with improved migration resistance, it may further include an additive selected from the group consisting of stabilizers, fillers and the like.

According to one embodiment, in the resin composition with improved migration resistance, it may include 30 to 50 parts by weight of the plasticizer and 0.1 to 20 parts by weight of the alkyl acrylate oligomer 100 parts by weight of the resin.

According to another aspect of the present invention, a resin molded article having improved migration resistance can be provided. According to one embodiment, the resin molded article with improved migration resistance may be molded using the 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 the injection solution.

According to an embodiment of the present invention, when the alkyl acrylate oligomer having a predetermined molecular weight is included in the resin composition containing the conventional resin and the conventional plasticizer, the effect of solving the migration problem, which is the biggest disadvantage of the plasticizer, is exceptional. Do. In particular, the alkyl acrylate oligomer is included in a composition containing a phthalate plasticizer widely used in the art, and the effect of inhibiting the transition of the phthalate plasticizer is very particular.

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

According to an embodiment of the present invention, a resin composition including a resin, a plasticizer, and an alkyl acrylate oligomer having a predetermined molecular weight is excellent in heat resistance and transition resistance while maintaining excellent physical properties such as transparency, hardness, elongation, and fluidity of the resin. At the same time can improve the effect.

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

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

Hereinafter, the present invention will be described in more detail with reference to the following examples, but the following examples are only for illustrating the present invention, and the scope of the present invention is not limited thereto.

The embodiments of the present invention are provided to more fully explain the present invention to those skilled in the art, and the following examples can be modified in various other forms, and the scope of the present invention is It is not limited to an Example. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the inventive concept to those skilled in the art.

Also, as used herein, the term "aliphatic" refers to compounds belonging to an organic class in which the valences are not linked together to form an aromatic ring. As one of the main structural groups of organic molecules, the aliphatic compounds include alkanes comprising linear, branched, cyclic, and substances derived from 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 which is one of a large class of unsaturated chemical compounds characterized by one or more planar rings bonded by covalent bonds, with some alternating single or double bonds. And the characteristic properties of these compounds are aromatic. Directivity results in a specific bond arrangement that allows for the inclusion of π (pi) electrons in strongly open molecules. Benzene, toluene and naphthalene are the best known aromatic compounds and form the parent of other aromatic compounds.

Also, the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the scope of the invention. In addition, although described in the singular in this specification, a plural form may be included unless the singular is clearly indicated in the context. Also, as used herein, the terms "comprise" and / or "comprising" specify the shapes, numbers, steps, actions, members, elements and / or presence of these groups. It does not exclude the presence or addition of other shapes, numbers, operations, members, elements and / or groups.

In addition, the term "phr" (phr) as used herein is a unit indicating the content of the resin composition, and represents the weight of each component included on the basis of 100 parts by weight of resin. In preparing the resin composition of the present embodiment, 100 parts by weight of resin is used, 50 parts by weight of DEHP plasticizer is used based on 100 parts by weight of the resin, and an alkyl acrylate oligomer may be prepared using 5 parts by weight or 10 parts by weight.

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

The present invention provides a resin composition comprising a conventional resin and a conventional plasticizer, wherein the plasticizer is leached from the resin and is released to the outside, so as to solve the problem of 'migration property'. The present invention relates to a resin composition for improving mechanical properties and thermal stability at the same time and a resin molded article prepared therefrom.

According to one embodiment of the present invention, a resin composition having improved performance may 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 the resin, 30 to 80 parts by weight of the plasticizer and 0.1 to 20 parts by weight of the alkyl acrylate oligomer.

The resin included 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 thermoplastic resin may be used universally.

More specifically, the resin may be polyvinyl chloride (PVC). The polyvinyl chloride (PVC) can be a homopolymer, copolymer, polyvinyl dichloride (PVDC) or similar polymers thereof. In addition, the polyvinyl chloride (PVC) may be a 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 may be used universally as an ester plasticizer. The ester plasticizer may be obtained through esterification 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, may include adipic acid, phthalic acid, trimellitic acid, and the like. 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, isodecyl Alcohols and the like.

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

In addition, the ester plasticizer may be one or two or more selected from the group consisting of the adipate-based plasticizer, phthalate-based plasticizer and trimellitate-based 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 40 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 is contained in 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 in an amount of 50 parts by weight or less based on 100 parts by weight of the resin by improving the plasticizer's migration resistance. That is, according to this invention, even if it contains a small amount of plasticizers in a resin composition, there exists an advantage which can expect sufficient plasticization effect.

The alkyl acrylate oligomer included in the resin composition of the present invention may act as a compatibilizer to improve compatibility between the resin and the plasticizer, thereby acting as a migration inhibitor of the plasticizer. In addition, the alkyl acrylate oligomer has a solubility parameter in the range of 16 to 20. Since the said alkyl acrylate oligomer solubility coefficient has an approximation compared with the theoretical solubility coefficient which a normal resin or a plasticizer has, it is judged that it is excellent in compatibility with these resins or a plasticizer. The migration resistance of the alkyl acrylate oligomer is very effective when 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 bonded to an alkyl group having 1 to 15 carbon atoms, 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 formula (1) or 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, and R ¹ , R ² and R ³ are the same or different 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 a small amount of less than 0.1 parts by weight, the addition effect thereof cannot be expected. In addition, the content of the alkyl acrylate oligomer is in excess of 20 parts by weight, and may be a factor for lowering the physical properties of the resin composition or the resin molded article.

The resin composition of the present invention may further include an additive selected from the group consisting of stabilizers, fillers and the like. The selection and content of these additives may be appropriately adjusted within the range allowed in the art, and the present invention does not particularly limit the selection and content of these additives.

The stabilizer may be added to prevent the resin and / or plasticizer from being degraded by heat, light or oxygen in the air under the use environment. The stabilizer is a general-purpose, lead sulfate which is a metal-based stabilizer; Stearic acid salts such as lead stearate, cadmium stearate, magnesium stearate, calcium stearate, zinc stearate, barium stearate, a complex stearate of calcium and zinc; Tin compounds such as dibutyl tin laurate and dibutyl tin sulfonate; Carbonates such as aluminum carbonate, magnesium carbonate, and composite carbonates of aluminum and magnesium; Phenolic compounds; Phosphoric acid ester compounds; Or phosphorous acid ester compounds; It may include one or two or more selected from the group consisting of. The stabilizer can be appropriately selected depending on the intended use. The stabilizer may be included in 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. If the amount of the stabilizer exceeds 10 parts by weight of excess, more than necessary thermal stability may be expressed.

The filler is a conventional one used in the art, specifically, may include one or two or more selected from the group consisting of calcium carbonate, diatomaceous earth, cray and talc. In addition, the filler may include naturally occurring silicates or natural carbonates. The filler may be included in less than 50 parts by weight, more specifically in the range of 10 to 30 parts by weight based on 100 parts by weight of the resin constituting the resin composition. If the content of the filler exceeds 50 parts by weight, the excess may be a factor that lowers the tensile strength, elongation, processability and the like.

According to another embodiment of the present invention, a resin molded article having improved migration resistance manufactured using the above-described resin composition may be provided.

The resin composition has excellent properties of improved heat resistance and migration resistance while maintaining excellent physical properties such as transparency, hardness, elongation, fluidity, and the like. The resin composition may be useful as a molding material for molding into a film, tube, pipe, cable insulation, artificial leather, wallpaper, gloves, toys and medical containers. In particular, since the resin composition has excellent migration resistance, it can be preferably used as a molding material for molding a medical tube for injecting an injection solution.

The method for producing a resin molded article using the resin composition may be carried out by a molding method of? V phase, this molding method may be applied to a method widely used in the art. This invention does not put a restriction on the method of manufacturing a resin molded article using the said resin composition.

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

EXAMPLE

Synthesis Example . Alkyl Acrylate  Synthesis of Oligomers

Alkyl acrylate oligomers were synthesized using GTP polymerization (Group transfer polymerization) or radical polymerization (Radical polymerization).

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

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

The flask was connected to a dropping funnel and a temperature sensor of a thermal stirrer and purged with nitrogen. 0.04 g of tetrabutylammonium 3-chlorobenzoate (TBACB) catalyst, 1.74 g of methyl trimethylsilyl dimethyl ketene acetal as GTP initiator, 2.49 g of THF and 0.4 g of acetonitrile were added to the flask, followed by stirring at room temperature at 700 rpm. Stirred 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 performed for 5 hours at 700 rpm stirring at room temperature. During the reaction, the molecular weight and the dispersion degree (PDI) of the oligomers produced were monitored by gel permeation chromatography (GPC), and after confirming that the molecular weight was close to the target molecular weight, methanol was added to terminate the polymerization reaction. After the completion of the polymerization, the mixture was washed with 50% ethanol aqueous solution and dried to obtain an oligomeric product (conversion: 95% or more, yield: 90%).

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

Radical polymerization was used to synthesize butyl acrylate oligomers having a number average molecular weight of 1,800 g / mol and 2,500 g / mol. Specific synthesis method is as described later.

After connecting the temperature sensor of the reflux condenser and 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) were added as a radical initiator, and then chained. As the transfer agent, 3.4 g (target molecular weight 1,800 g / mol) or 2.44 g (target molecular weight 2,500 g / mol) of dodecanethiol was added thereto. Thereafter, the toluene reaction solvent was added at a weight ratio of 30%. The reaction mixture was allowed to proceed with stirring while stirring at a temperature of 115 ° C. at 800 rpm. During the reaction, the molecular weight and the dispersion degree (PDI) of the oligomers produced were monitored by gel permeation chromatography (GPC). After confirming that the oligomers were 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 using 50% ethanol aqueous solution, and the reactant having a target number average molecular weight of 2,500 g / mol was washed by a solvent fractionation method based on normal hexane. After washing, it was dried to obtain an oligomeric product (conversion: 80%, yield: 65%).

Molecular weight and dispersion degree (PDI) of each of the butyl acrylate oligomers (pBA) obtained in Synthesis Examples 1 to 3 were measured and shown 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 oligomer (pBA) obtained in Synthesis Examples 1 to 3 has a narrow molecular weight distribution of PDI less than 2.

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

3 to 5 also attached ¹ H-NMR spectra for each of the butyl acrylate oligomers (pBA) obtained in Synthesis Examples 1 to 3.

3 is a spectrum of pBA1000 synthesized by the GTP polymerization method according to Synthesis Example 1. According to FIG. 3, the butyl end of Ha was characteristically present at 0.9 ppm, the Hh next to the ester functional group was 4.0 ppm, and the second and third alkyl groups of the butyl group and Hc, Hd, He and Hf of the polymer backbone were 1.2. Characterized at from-2.5 ppm. In addition, Hb and Hg derived from the GTP initiator were characteristically identified at 1.1 and 3.6 ppm, respectively.

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

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

Reference Example : For PVC or DEHP plasticizer Alkyl Acrylate  Determination of compatibility of oligomer

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

Table 2 shows the results of mixing the polyvinyl chloride (PVC) and the alkyl acrylate oligomer in a 1: 1 weight ratio and evaluating compatibility after 24 hours.

Evaluation of Compatibility of Alkyl Acrylate Oligomers for PVC division Theoretical solubility factor Compatibility judgment for PVC PVC Alkyl acrylates
Oligomer PVC / pBA1000 19.95 17.63 Excellent PVC / pBA1800 17.11 Excellent PVC / pBA2500 16.77 Excellent

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

Evaluation of Compatibility of Alkyl Acrylate Oligomers with DEHP Plasticizer division Theoretical solubility factor Compatibility Determination for DEHP DEHP plasticizer Alkyl acrylates
Oligomer DEHP / pBA1000 18.51 17.63 Excellent DEHP / pBA1800 17.11 Excellent DEHP / pBA2500 16.77 Excellent

According to Tables 2 and 3, the alkyl acrylate oligomer synthesized in Synthesis Examples 1 to 3 can be confirmed that the theoretical solubility coefficients are close to each other when compared with PVC or DEHP plasticizer. Therefore, the alkyl acrylate oligomer synthesized in Synthesis Examples 1 to 3 is judged to have excellent compatibility with the thermoplastic resin and the plasticizer.

Comparative example  1 and Example  1 to 6: Preparation of Resin Composition

A resin composition containing butyl acrylate oligomers synthesized in Synthesis Examples 1 to 3 was prepared. Table 4 below shows the compositional components and the composition ratios constituting the resin composition.

As the resin, polyvinyl chloride (PVC; KL-10, Hanwha Chemical Co., Ltd.) was selected as the resin, and di (2-ethylhexyl) phthalate (DEHP; Sigma Aldrich Co., Ltd.) was selected as the plasticizer as the phthalate plasticizer. It was. Songwon Industrial's thermal stabilizer (SONGSTAB ™ BZ-119) was used as an additive. In the present embodiment, PVC is used as the thermoplastic resin and DEHP is used as the plasticizer. However, 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 compositions prepared in Comparative Example 1 and Examples 1 to 6, the following experiment was carried out.

Experimental Example 1. Evaluation of transmittance of the resin composition

In order to evaluate the transmittance of the resin compositions prepared in Comparative Example 1 and Examples 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 barrier rib (150 * 150 * 15 mm) formed on a glass substrate. After removing most of the THF solvent at room temperature and gelled at 75 ℃ for 30 minutes, a transparent soft PVC film with an average thickness of 0.15 mm was prepared.

In order 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.

In FIG. 6, compared to the film of Comparative Example 1, in which the butyl acrylate oligomer was not added, the butyl acrylate oligomer (pBA1000, pBA1800, pBA2500) was shown in a graph comparing the transmittance of each film containing 10 parts by weight. According to Figure 6, it can be seen that the introduction of butyl acrylate oligomer has little effect on the permeability of the soft PVC film. That is, the added butyl acrylate oligomer is excellent in compatibility with the 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 thereof.

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

In order to evaluate the thermal properties of the resin compositions 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.

To evaluate how the introduction of butyl acrylate oligomers affects the thermal properties of soft PVC films, dynamic kinetic analysis (DMA, DMA / SS6100, Seiko Exstar) and thermogravimetric analyzer (TGA, Q50, TA Analysis) Glass transition temperature was measured using.

7 and Table 5 show the results of measuring the glass transition temperature of the flexible 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, in contrast to the film of Comparative Example 1 in which the butyl acrylate oligomer was not added, the film containing 10 parts by weight of the butyl acrylate oligomer (pBA1000, pBA1800, pBA2500), respectively, had a glass transition temperature ( It can be seen that Tg) is lowered by about 10 ℃. In addition, it was confirmed that the Tg change due to the change in the molecular weight of the butyl acrylate oligomer is insignificant. These results indicate that the butyl acrylate oligomer itself has a plasticizing effect on PVC, and thus, it is considered that the free volume is significantly increased than when using DEHP alone.

In addition, FIG. 8 and Table 6 show the results of monitoring the temperature of 10% weight loss (Td10) of the soft PVC film by a thermogravimetric analyzer (TGA).

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

8 and Table 6, in contrast to the film of Comparative Example 1 in which the butyl acrylate oligomer was not added, the film containing 10 parts by weight of the butyl acrylate oligomer (pBA1000, pBA1800, pBA2500) of about 10 parts by weight of Td10 It can be confirmed that the temperature rises. These results suggest that the butyl acrylate oligomer is well bound in PVC through the polar bonding with the DEHP plasticizer, thereby reducing the heat transfer to the film surface and reducing the subsequent volatilization of DEHP.

Experimental Example 3. Shore A hardness evaluation of resin composition

In order to evaluate how the introduction of butyl acrylate oligomers affect the plasticity of the PVC composition, Shore A hardness was measured after making 30 * 30 * 15 mm specimens according to ASTM D2240. The results are shown in FIG.

According to FIG. 9, in contrast to the specimen without the butyl acrylate oligomer, the specimen containing 10 parts by weight of butyl acrylate oligomer (pBA1000, pBA1800, pBA2500), respectively, shows almost no difference in the Shore A hardness within ± 1. can confirm. That is, the added butyl acrylate oligomer is excellent in compatibility with the 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 assess how the introduction of butyl acrylate oligomers affects the elongation of PVC compositions, after making 24.5 * 100 * 0.150 mm specimens in accordance with ASTM D882, a universal testing machine (UTM, LR30K, LLOYD Instruments) was used. Elongation was measured. The results are shown in FIG.

According to FIG. 10, in contrast to the specimen without the butyl acrylate oligomer added, the specimens each containing 10 parts by weight of the butyl acrylate oligomer (pBA1000, pBA1800, pBA2500) have almost no difference in elongation. That is, the added butyl acrylate oligomer is excellent in compatibility with the PVC resin and DEHP plasticizer, it can be seen that there is no fear of lowering the elongation of the PVC composition due to the addition thereof.

Experimental Example 5. Evaluation of Performance Resistance of Resin Composition

In order to evaluate how the introduction of butyl acrylate oligomers affects the migration properties of PVC compositions, 50 * 50 * 0.150 mm specimens were fabricated according to ASTM D1239. The prepared specimens were placed in 70 ° C. deionized water for 24 hours, and then evaluated for transferability by weight measurement. In addition, the prepared specimens were placed in 25 ° C. 50% ethanol aqueous solution for 24 hours, and then evaluated for transferability through weight measurement. Based on the result of evaluating plasticizer transferability in two solvent systems of deionized water or ethanol aqueous solution, the degree of transition was measured based on Equation 1 below. The degree of migration measured in both solvent systems is shown in FIGS. 11 and 12, respectively.

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

11 and 12, the specimens containing 5 parts by weight or 10 parts by weight of the butyl acrylate oligomer (pBA1000, pBA1800, pBA2500), respectively, compared to the specimen without the butyl acrylate oligomer added 41 to 41 45% reduction. 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 the butyl acrylate oligomer having a relatively higher molecular weight, the free volume is increased to partially offset the polar bonding effect between the butyl acrylate and the DEHP plasticizer, and thus, the transition of the plasticizer is more likely to proceed. 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 (11)

Suzy;
Plasticizers; And
Alkyl acrylate oligomers having a number average molecular weight of 500 to 5,000 g / mol;
The resin composition improved the migration resistance comprising a. The method of 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) with improved migration resistance. Resin composition. The method of claim 1,
The resin is a polyvinyl chloride (PVC) resin composition with improved migration resistance. The method of claim 1,
The plasticizer is a resin composition with improved migration resistance, which is an ester plasticizer obtained by reacting a polycarboxylic acid compound and a linear or branched aliphatic alcohol compound having 3 to 15 carbon atoms. The method of claim 1,
The plasticizer is dibutyl phthalate (DBP), di (2-ethylhexyl) phthalate (DEHP), dioctyl phthalate (DOP), di (isononyl) phthalate (DINP), di (2-propylheptyl) phthalate (DPHP) And phthalate plasticizers selected from the group consisting of di (isodecyl) phthalate (DIDP); Adipate-based plasticizers selected from the group consisting of dioctyl adipate (DOA) and di (isononyl) adipate (DINA); Trimellitate plasticizers selected from the group consisting of tri (2-ethylhexyl) trimellitate, trioctyl trimellitate and tridecyl trimellitate; And cyclohexane-based plasticizers, wherein the resin composition is improved in one or two or more kinds selected from the group consisting of plasticizers. The method of claim 1,
The plasticizer is a phthalate-based plasticizer is improved resin composition. The method of claim 1,
The alkyl acrylate oligomer is a compatibilizer for improving the compatibility between the resin and the plasticizer, and improved resin composition which acts as a migration inhibitor of the plasticizer. The method of claim 1,
The resin composition with improved migration resistance of the solubility parameters of the alkyl acrylate oligomer is 16 to 20. The method of claim 1,
The alkyl acrylate oligomer is a polymer of an alkyl acrylate monomer bonded to an alkyl group having 1 to 15 carbon atoms, and has a number average molecular weight of 500 to 5,000 g / mol. The method of claim 1,
The alkyl acrylate oligomer is a butyl acrylate oligomer having a number average molecular weight of 1,000 to 3,000 g / mol of the resin composition with improved migration resistance. The method of claim 1,
The alkyl acrylate oligomer is a resin composition with improved migration resistance represented by the following formula (1) or (2).

Images