Thermoplastic resin composition having self-healing characteristics, and molded product using same

Abstract

The present invention relates to a thermoplastic resin composition having self-healing characteristics, comprising: a continuous phase including an ionomer composition; and a dispersed phase including a rubber composition, wherein the ionomer composition comprises ethylene, which is functionalized with a first polar group, and a first neutralization metal, the first neutralization metal comprises at least two metals having different valences, the rubber composition comprises an unsaturated rubber, which is functionalized with a second polar group, and a second neutralization metal, and the second neutralization metal comprises at least two metals having different valences.

Description

Thermoplastic resin composition having self-healing properties and molded article using the same

[0001] The present invention relates to a thermoplastic resin having scratch self-restoration performance and excellent strength such as hardness and tensile strength, as well as product formability and elasticity, and a molded product using the same.

[0002] In general, materials that can provide comfort, luxury, and excellent tactile sensation to the body contact areas of the car are used in automobile interior materials such as door trim, dashboard, instrument panel, console, and floor carpet.

[0003] Recently, as part of the trend toward high-end automotive interior parts, many are adopting black high-gloss specifications. However, the scratches that occur when high-gloss is applied are reducing marketability and increasing consumer dissatisfaction.

[0004] In general, most scratches on automobile interior parts are caused by everyday life by consumers. However, research is being conducted on minimizing scratches to achieve high-quality automobile interior parts.

[0005] In this regard, research has been conducted to prevent scratches by increasing the hardness of the coating, or to increase the hardness by using nano-sized silica or alumina as disclosed in Japanese Patent Application Laid-Open No. 2000-293895 (Patent Document 1). However, there is a limit to scratch prevention, and there is a problem that scratches that have occurred do not disappear.

[0006] In addition, as disclosed in Korean Patent Registration No. 10-0643335 (Patent Document 2), scratch self-recovery performance was attempted to be realized by utilizing the elasticity of the urethane molecular structure formed by reacting acrylic, aliphatic polyester, etc. with isocyanate. However, the physical properties were poor, so they did not satisfy the physical properties of automobile interior parts, and the drying speed was slow, making it difficult to use for industrial purposes.

[0007] Patent Document 1: Japanese Patent Application Laid-Open No. 2000-293895

[0008] Patent Document 2: Korean Patent Publication No. 10-0643335

[0009] Accordingly, the present invention aims to solve the above-mentioned problems by providing a thermoplastic resin having excellent scratch self-healing performance, mechanical strength such as hardness and tensile strength, as well as excellent product formability and elasticity.

[0010] The present invention aims to provide a molded product having a high scratch recovery rate and enhanced scratch resistance by using a thermoplastic resin composition having the above self-healing properties.

[0011] In addition, the present invention seeks to provide a molded product capable of realizing soft feeling and high strength at low hardness.

[0012] The present invention relates to a thermoplastic resin composition having self-healing properties, comprising a continuous phase comprising an ionomer composition; and a dispersed phase comprising a rubber composition, wherein the ionomer composition comprises ethylene functionalized with a first polar group and a first neutralizing metal, wherein the first neutralizing metal comprises two or more kinds of metals having different valences, and the rubber composition comprises an unsaturated rubber functionalized with a second polar group and a second neutralizing metal, wherein the second neutralizing metal comprises two or more kinds of metals having different valences.

[0013] In one embodiment of the present invention, each of the first neutralizing metal and the second neutralizing metal may include at least one monovalent metal ion and at least one divalent metal ion.

[0014] In one embodiment of the present invention, each of the first neutralizing metal and the second neutralizing metal may include at least two or more metals selected from lithium, sodium, potassium, magnesium, calcium, and zinc.

[0015] In one embodiment of the present invention, each of the first neutralizing metal and the second neutralizing metal may include two or more metals selected from sodium, magnesium, and zinc metals.

[0016] In one embodiment of the present invention, each of the first neutralizing metal and the second neutralizing metal may contain sodium and zinc in a ratio of 9:1 to 1:9.

[0017] In one embodiment of the present invention, each of the first neutralizing metal and the second neutralizing metal may contain sodium and magnesium in a ratio of 9:1 to 1:9.

[0018] In one embodiment of the present invention, the first and second neutralizing metals may include the same type of metal.

[0019] In one embodiment of the present invention, the continuous phase may be comprised of 20 to 95 parts by weight; and the dispersed phase may be comprised of 80 to 5 parts by weight.

[0020] In one embodiment of the present invention, the ionomer composition can be prepared by mixing 1 to 30 parts by weight of the first polar group and 1 to 30 parts by weight of the first neutralizing metal with respect to 100 parts by weight of ethylene.

[0021] In one embodiment of the present invention, the rubber composition can be prepared by mixing 1 to 20 parts by weight of a second polar group and 1 to 20 parts by weight of a second neutralizing metal with respect to 100 parts by weight of unsaturated rubber.

[0022] In one embodiment of the present invention, the ionomer composition and the rubber composition may each include at least one selected from an initiator, a crosslinking agent, an antioxidant, a lubricant, a catalyst, and a UV stabilizer.

[0023] In one embodiment of the present invention, the unsaturated rubber may be at least one selected from the group consisting of polyisoprene rubber, polybutadiene rubber, ethylene propylene diene EPDM rubber (ethylene propylene diene monomer rubber), styrene butadiene rubber, and acrylonitrile butadiene rubber.

[0024] In one embodiment of the present invention, the first polar group and the second polar group may each be independently selected from the group consisting of acrylic acid, methacrylic acid, carboxylic acid, and polycarboxylic acid comprising two or more COOH carboxyl groups.

[0025] In one embodiment of the present invention, the polycarboxylic acid containing two or more COOH carboxyl groups may be selected from the group consisting of malonic acid, succinic acid, glutaric acid, pimelic acid, itaconic acid, and adipic acid.

[0026] One embodiment of the present invention provides a molded article manufactured from a thermoplastic resin composition having the self-healing properties described above.

[0027] In one embodiment of the present invention, the molded product may be selected from automotive interior and exterior materials, electronic products, leisure products, and golf balls.

[0028] The present invention provides a thermoplastic resin composition and a molded article manufactured therefrom, which exhibits superior self-healing performance, scratch resistance, and mechanical properties by utilizing two or more types of metals with different valences. These molded articles possess properties suitable for use in automotive interior materials, and their scratch-recovery properties can extend the service life of interior materials.

[0029] FIG. 1 shows the results of an evaluation of the scratch recovery rate for the thermoplastic resin composition of Example 20 as an embodiment of the invention.

[0030] FIG. 2 and FIG. 3 are examples of one embodiment of the present invention, showing the evaluation of scratch resistance for the thermoplastic resin compositions of Example 20 and Comparative Example 1.

[0031] A thermoplastic resin composition having self-healing properties according to an embodiment of the present invention comprises a continuous phase comprising an ionomer composition; and a dispersed phase comprising a rubber composition, wherein the ionomer composition comprises ethylene functionalized with a first polar group and a first neutralizing metal, wherein the first neutralizing metal comprises at least one monovalent metal and at least one divalent metal ion, and the rubber composition comprises an unsaturated rubber functionalized with a second polar group and a second neutralizing metal, wherein the second neutralizing metal comprises at least one monovalent metal and at least one divalent metal ion.

[0032] Hereinafter, the term “self-healing” or “self-restoration” or “self-regeneration” is used herein to mean a property or performance that enables a polymer damaged by an external environment to detect a defect on its own, repair its structure, and recover its original function.

[0033] In this application, the terms “functionalized,” “modified,” or “grafted” are used interchangeably and are considered interchangeable.

[0034] Hereinafter, embodiments of the present invention will be described in detail. However, these are presented as examples and are not intended to limit the present invention. The present invention is defined solely by the scope of the claims set forth below.

[0035] The present invention provides a thermoplastic resin composition having self-healing properties, comprising a continuous phase comprising an ionomer composition; and a dispersed phase comprising a rubber composition, wherein the ionomer composition comprises ethylene functionalized with a first polar group and a first neutralizing metal, wherein the first neutralizing metal comprises two or more kinds of metals having different valences, and the rubber composition comprises an unsaturated rubber functionalized with a second polar group and a second neutralizing metal, wherein the second neutralizing metal comprises two or more kinds of metals having different valences.

[0036] In the present invention, the first neutralizing metal and the second neutralizing metal each independently include two or more types of metals having different valences.

[0037] In one embodiment of the present invention, the first neutralizing metal may include at least one monovalent metal and at least one divalent metal ion, and the second neutralizing metal may include at least one monovalent metal and at least one divalent metal ion.

[0038] In one embodiment of the present invention, the first neutralizing metal may include at least two kinds of metals selected from lithium, sodium, potassium, magnesium, calcium, and zinc, and preferably may include two kinds of metals selected from sodium, magnesium, calcium, and zinc. More preferably, the first neutralizing metal includes two kinds of metals selected from sodium, magnesium, and zinc.

[0039] In a preferred embodiment of the present invention, the first neutralizing metal may include sodium and zinc in a ratio of 9:1 to 1:9, preferably sodium and zinc in a ratio of 3:1 to 1:3. In addition, the first neutralizing metal may include sodium and magnesium in a ratio of 9:1 to 1:9, preferably sodium and magnesium in a ratio of 3:1 to 1:3. In this case, the self-healing characteristics and mechanical properties of the thermoplastic resin composition are improved.

[0040] The second neutralizing metal may include at least two kinds of metals selected from lithium, sodium, potassium, magnesium, calcium, and zinc, and preferably may include two kinds of metals selected from sodium, magnesium, calcium, and zinc. More preferably, the second neutralizing metal includes two kinds of metals selected from sodium, magnesium, and zinc.

[0041] In a preferred embodiment of the present invention, the second neutralizing metal may include sodium and zinc in a ratio of 9:1 to 1:9, preferably sodium and zinc in a ratio of 3:1 to 1:3. In addition, the second neutralizing metal may include sodium and magnesium in a ratio of 9:1 to 1:9, preferably sodium and magnesium in a ratio of 3:1 to 1:3. In this case, the self-healing characteristics and mechanical properties of the thermoplastic resin composition are improved.

[0042] The first neutralizing metal and the second neutralizing metal may include the same or different types of metals, and preferably, the same types of metals are used as the first neutralizing metal and the second neutralizing metal. In one embodiment of the present invention, the first neutralizing metal and the second neutralizing metal may include two or more types of the same metal selected from sodium, magnesium, and zinc.

[0043] The thermoplastic resin composition according to the present invention has scratch self-healing properties by means of supramolecular attraction utilizing ionic bonding, a type of non-covalent bonding between a continuous phase and a dispersed phase. Ionic bonding is stronger than hydrogen bonding or covalent bonding and has the characteristic of being able to bond and dissociate due to changes in the fluidity between molecules. The ionic bonding introduced in the present invention forms non-permanent ionic cross-linking by the strong bonding force of Coulombic interaction, which is an interaction due to electrostatic attraction between ions, thereby exhibiting self-healing properties of the thermoplastic resin composition and imparting excellent mechanical properties such as hardness and tensile strength.

[0044] The thermoplastic resin composition according to the present invention not only has very high scratch resistance due to ionic bonding between or within the continuous phase and the dispersed phase, but also forms a supramolecular network through ionic bonding and covalent bonding between molecules, thereby restoring bonds or attractive forces within a broken polymer material.

[0045] The supramolecular network formed by the above ionic bonds and covalent bonds between molecules is formed by ion multiplets and / or clusters. The multiplets are composed of strong cohesive ionic groups formed by ion pairs, and even when the thermoplastic resin melts and the ion pairs are disturbed, the multiplet state remains intact. The clusters are aggregates in which multiple multiplets are loosely bound and interact with each other, and they not only have a strong cross-linking function but also act as fillers. Due to these characteristics, the thermoplastic resin composition of the present invention exhibits self-healing properties that attempt to recover from damage and excellent mechanical properties.

[0046] Furthermore, when the thermoplastic resin composition of the present invention uses two or more different metal ions, particularly two or more metals having different valences, as the first neutralizing metal and the second neutralizing metal in the continuous phase ionomer composition and the dispersed phase rubber composition, it is expected to further enhance the bonding force between the multiplets and / or clusters. As a result, it was confirmed that the self-healing characteristics, scratch resistance characteristics, and mechanical properties of the thermoplastic resin composition are significantly improved. It is believed that when the first neutralizing metal and the second neutralizing metal include two or more different metals having different valences, the self-healing performance, scratch resistance, elasticity, and other physical properties are further improved due to the synergistic effect of the size of the multiplets and clusters and the internal attractive bonding.

[0047] In one embodiment, the thermoplastic resin may comprise 20 to 95 parts by weight of the continuous phase and 80 to 5 parts by weight of the dispersed phase. Preferably, it may comprise 30 to 70 parts by weight of the continuous phase and 70 to 30 parts by weight of the dispersed phase, and more preferably, it may comprise 40 parts by weight of the continuous phase and 60 parts by weight of the dispersed phase.

[0048] In one embodiment, the ionomer composition constituting the continuous phase can be prepared by mixing 1 to 30 parts by weight of the first polar group and 1 to 30 parts by weight of the first neutralizing metal with respect to 100 parts by weight of ethylene.

[0049] In one embodiment, the rubber composition constituting the dispersed phase can be prepared by mixing 1 to 20 parts by weight of the second polar group and 1 to 20 parts by weight of the second neutralizing metal with respect to 100 parts by weight of the unsaturated rubber.

[0050] Specific embodiments of the present invention are presented below. However, the embodiments described below are merely intended to specifically illustrate or explain the present invention and should not be construed as limiting the present invention.

[0051]

[0052] (A) Ionomer composition

[0053] The ionomer composition according to the present invention comprises ethylene functionalized with a first polar group and a first neutralizing metal.

[0054] The ethylene functionalized with the first polar group is a copolymer of ethylene and the first polar group, and forms an intermolecular ionic cluster through ionic bonding with the first neutralizing metal. For example, a polyethylene-methacrylic acid ionomer can be formed through copolymerization of ethylene and the first polar group, methacrylic acid (see Figure 1), and it forms an ion pair with the first neutralizing metal cation (sodium ion) to generate electrostatic attraction, ultimately resulting in excellent mechanical properties through ionic cross-linking formed in a highly stabilized state.

[0055] Figure 1

[0056]

[0057]

[0058] In one embodiment, the ionomer composition can be prepared by mixing 1 to 30 parts by weight of the first polar group and 1 to 30 parts by weight of the first neutralizing metal with respect to 100 parts by weight of ethylene.

[0059]

[0060] The first polar group is selected from the group consisting of acrylic acid, methacrylic acid, carboxylic acid and polycarboxylic acid containing two or more COOH carboxyl groups, and is preferably a polycarboxylic acid containing two or more COOH carboxyl groups. The polycarboxylic acid includes malonic acid, succinic acid, glutaric acid, pimelic acid, itaconic acid or adipic acid, and is particularly preferably itaconic acid or adipic acid. The first polar group enables ionic cross-linking, and at this time, not only improves the scratch recovery rate of the thermoplastic resin, but also improves the mechanical properties.

[0061] The above first polar group may be included in an amount of 1 to 30 parts by weight, and preferably 1 to 20 parts by weight, based on 100 parts by weight of the ethylene. When the above range is satisfied, mechanical properties are improved and scratch recovery rate is enhanced.

[0062] For 100 parts by weight of the ethylene, the first neutralizing metal is preferably included in an amount of 1 to 30 parts by weight. If the content of the first neutralizing metal is less than 1 part by weight, sufficient ionic bonding is not formed between the ethylene functionalized with the first polar group and the first neutralizing metal, making it difficult to improve mechanical properties compared to a conventional composition. If it exceeds 30 parts by weight, there is a concern that the properties of the thermoplastic resin composition may deteriorate or an unreacted material may remain due to a problem with the dispersibility of the first neutralizing metal.

[0063]

[0064] (B) Rubber composition

[0065] The thermoplastic resin composition of the present invention includes a rubber composition to improve soft touch and scratch resistance, and the rubber composition includes an unsaturated rubber functionalized with a second polar group and a second neutralizing metal.

[0066] The above unsaturated rubber is modified with a second polar group capable of ionic bonding, and in one embodiment, the unsaturated rubber can be obtained by adding the second polar group and an initiator to the unsaturated rubber and reacting them. More specifically, in one embodiment, the rubber composition can be prepared by mixing 1 to 20 parts by weight of the second polar group and 1 to 20 parts by weight of the second neutralizing metal with respect to 100 parts by weight of the unsaturated rubber.

[0067] The second polar group is selected from the group consisting of acrylic acid, methacrylic acid, carboxylic acid and polycarboxylic acid containing two or more COOH carboxyl groups, and is preferably a polycarboxylic acid containing two or more COOH carboxyl groups. The polycarboxylic acid includes malonic acid, succinic acid, glutaric acid, pimelic acid, itaconic acid or adipic acid, and is particularly preferably itaconic acid or adipic acid. The unsaturated rubber modified with the polycarboxylic acid containing two or more COOH carboxyl groups forms an ionic bond with the ionomer and thus has self-healing performance, and thus has an excellent scratch recovery rate.

[0068] The above second polar group may be included in an amount of 1 to 20 parts by weight per 100 parts by weight of the unsaturated rubber, and preferably, 1 to 10 parts by weight. When the above range is satisfied, mechanical properties are improved and scratch recovery rate is enhanced.

[0069] The above unsaturated rubber refers to a rubber that can react with a second polar group including an unsaturated group, and may be, for example, at least one selected from the group consisting of polyisoprene rubber, polybutadiene rubber, ethylene propylene diene EPDM rubber (ethylene propylene diene monomer rubber), styrene butadiene rubber, and acrylonitrile butadiene rubber. Preferably, the above unsaturated rubber is styrene butadiene rubber and EPDM rubber.

[0070] The second neutralizing metal forms an ionic bond with the second polar group functionalized in the unsaturated rubber, resulting in the formation of ionic clusters between unsaturated rubber molecules through ion-ion interaction. Furthermore, the ionic clusters formed between rubber molecules interact with the ionomer through ionic bonds to form a supramolecular complex network, significantly enhancing self-healing ability.

[0071] In one embodiment of the present invention, the thermoplastic resin composition may additionally include about 0.1 to 5 parts by weight of one or more additives selected from an initiator, a crosslinking agent, an antioxidant, a lubricant, a catalyst, and a UV stabilizer.

[0072] The above initiator is a substance for initiating a polymerization reaction, preferably a functionalization reaction, of the ionomer composition and the rubber composition. Any initiator commonly used in the art may be used, and preferably, t-butylcumyl peroxide, benzoyl peroxide, cumene hydroperoxide, dicumyl peroxide, methyl ethyl ketone peroxide, 2,5-dimethyl-2,5-di(t-butyl peroxy)hexane, di-t-butyl peroxide, t-butylperoxybenzoate, a,a-bis(t-butyl peroxyisopropyl)benzene, di-isopropylbenzene, or a mixture thereof is used. In addition, it is preferable to use the initiator in an amount of 0.05 to 1.0 parts by weight based on the total weight of the resin composition. If the initiator is less than 0.05 parts by weight, a sufficient reaction does not occur, and if it exceeds 1.0 parts by weight, there is a problem that protrusions may occur due to an overreaction phenomenon, so it is preferable to use it within the above range.

[0073] The above cross-linking agent is for forming a three-dimensional network structure by forming a chemical bond between some specific atoms in the unsaturated rubber, and the types of peroxide-based cross-linking agents include 1,1-(t-butylperoxy)-3,3,5-trimethylcyclohexane (TMC), n-butyl-4,4-(bis-butyl peroxy)valerate (TVP), dicumyl peroxide (DCP), 1,1-bis(t-butylperoxy)-diisopropylbenzene (BPPB), benzoyl peroxide (BPO), t-butylperoxybenzoate (Z), di-t-butylperoxide (DTBP), 2,5-dimethyl-2,5-di-t-butylperoxyhexane (25B), 2,5-dimethyl-2,5-di-t-butylperoxyhexene-3 (hexyne-3), etc., but are not limited to cross-linking agents commonly used in the art. It can be used without.

[0074] The above antioxidants include phenol-based antioxidants, benzimidazole-based antioxidants, and amine-based antioxidants, and any antioxidant commonly used in the art can be used without limitation.

[0075] The above-mentioned lubricant is intended to reduce the viscosity of the rubber composition and increase processability, and may be used as a wax-based agent, such as PE wax or paraffin wax, or as a stearic acid-based agent, such as magnesium stearate or calcium stearate, either alone or in a mixture of two. In addition, it is preferable to use the lubricant in an amount of 0.5 to 2.0 parts by weight relative to the total weight of the resin composition. If the amount of the lubricant is less than 0.5 parts by weight, processability is poor, and if it exceeds 2.0 parts by weight, uniform dispersion may be hindered, and therefore it is preferable to use it within the above range.

[0076] The above catalyst is a catalyst for the crosslinking reaction of the rubber composition, and is not particularly limited as long as it is a catalyst commonly used in the art for this purpose, but it is preferably used in an amount of 0.5 to 3.0 parts by weight, and the amount used is preferably 0.5 to 5.0 parts by weight based on the total weight of the rubber composition. If the catalyst is less than 0.5 parts by weight, there is a problem that it does not sufficiently function as a crosslinking catalyst, and if it exceeds 5.0 parts by weight, there is a problem that crosslinking is not uniform and side reactions may occur, so it is preferably used within the above range.

[0077] The above UV stabilizer may be used without limitation as long as it is a UV stabilizer commonly used in the art, and it is preferable to use 0.5 to 5.0 parts by weight based on the total weight of the resin composition. If the UV stabilizer is less than 0.5 parts by weight, it is difficult to expect a sufficient UV stabilization effect, and if it exceeds 5 parts by weight, the UV stabilization effect is no longer achieved due to excessive use, and it may not only cause a decrease in the performance of the thermoplastic resin but also increase the cost, so it is used within the above range.

[0078] The thermoplastic resin composition may additionally include at least one thermoplastic resin, preferably an olefin-based resin, for hardness control. Examples of the olefin resin include polyolefin elastomers, α-olefin copolymers, thermoplastic elastomers, ethylene-vinyl acetate copolymers, polyamides, polyesters, polyurethanes, polyethers, metallocene polymers, styrene block copolymers, vinyl chloride resins, and vinylidene chloride resins.

[0079] A thermoplastic resin composition having self-healing properties has a scratch recovery rate of 50%, 60%, 70%, 80%, preferably 90% or more, and a hardness of Shore 30D, 40D, 50D, 60D, 70D, 80D, preferably 90D or less.

[0080] Another embodiment of the present invention provides a molded article manufactured from a thermoplastic resin composition having the self-healing properties. As an example, the molded article may be an automobile interior material.

[0081] Specific embodiments of the present invention are presented below. However, the embodiments described below are merely intended to specifically illustrate or explain the present invention and should not be construed as limiting the present invention.

[0082]

[0083] 1. Preparation of thermoplastic resin composition

[0084] Example 1

[0085] (Manufacture of continuous phase): Ethylene, an initiator, and a polar group were mixed according to the composition disclosed in Table 1 to modify ethylene, and then metal ions were added to prepare an ionomer composition. The composition was reaction-extruded using a twin-screw extruder to produce a continuous phase.

[0086] (Manufacture of dispersed phase): EPDM, an initiator, and a polar group were mixed according to the composition disclosed in Table 1 to modify unsaturated rubber, and then metal ions were added to prepare a rubber composition. This rubber composition was reaction-extruded using a twin-screw extruder to prepare a dispersed phase.

[0087] (Preparation of thermoplastic resin composition): A thermoplastic resin composition was prepared by mixing the continuous phase and the dispersed phase in the weight ratio described in Table 1.

[0088]

[0089] Examples 2 to 22 and Comparative Examples 1 to 11

[0090] A thermoplastic resin composition was prepared using the same method as in Example 1, but with different compositions as described in Tables 1 to 3.

[0091]

[0092] 2. Performance evaluation of thermoplastic resin compositions

[0093] The thermoplastic resin compositions manufactured in Examples 1 to 22 and Comparative Examples 1 to 11 were used to evaluate the physical properties according to the following method, and the results are listed in Tables 1 to 3.

[0094]

[0095] 1) Visual evaluation of scratch resistance

[0096] After producing a specimen measuring 60 mm in width x 60 mm in height x 3 mm in thickness, the specimen was scratched with a scraper at a distance of 100 mm under conditions of a load of 4.9 N and a speed of 100 mm / min, and then visually inspected to evaluate grades 1 to 5.

[0097]

[0098] Grade 1: Surface damage is significantly noticeable.

[0099] Grade 2: Surface damage is recognized.

[0100] Grade 3: Some surface damage is noticeable, but not severe.

[0101] Grade 4: Slight surface damage is noticeable.

[0102] Grade 5: No surface damage is recognized.

[0103]

[0104] 2) Hardness evaluation

[0105] Hardness was measured on the surface of the test specimen using a TECLOCK A Durometer according to ASTM D-2240.

[0106]

[0107] 3) Tensile strength evaluation

[0108] After making the manufactured test specimens approximately 2 mm thick, No. 4 test specimens were made according to ASTM D638, and the tensile strength and elongation were measured according to ASTM D638. At this time, five test specimens were used for the same test.

[0109]

[0110] 4) Scratch recovery rate evaluation

[0111] After producing a specimen measuring 60 mm in width x 60 mm in height x 3 mm in thickness, the specimen was scratched with a scraper under conditions of a load of 30 N and a speed of 100 mm / min, and the width was calculated under a microscope. After aging at 89°C for 24 hours, the width was calculated under a microscope to calculate the ratio of the restored width to the initial scratch width.

[0112] Meanwhile, Fig. 1 shows the results of a scratch recovery rate evaluation conducted on the thermoplastic resin composition of Example 20.

[0113] The five graphs on the left side of Fig. 1 are data obtained by calculating the width and area of ​​five selected damaged portions using a confocal microscope, and the five graphs on the left side of Fig. 1 are data obtained by recalculating the damaged portions for each of the five portions after aging for 24 hours. From this, it was found that the scratches in the five damaged portions present on the specimen manufactured with the thermoplastic resin composition of Example 20 were completely restored.

[0114]

[0115] 5) Scratch resistance (microscopic) evaluation

[0116] The scratch resistance of the thermoplastic resin compositions manufactured in Example 20 and Comparative Example 1 was evaluated and shown in FIGS. 2 and 3.

[0117]

[0118] A specimen measuring 60 mm in width x 60 mm in length x 3 mm in thickness was manufactured using the thermoplastic resin composition manufactured in Example 20 and Comparative Example 1, and then, under conditions of a speed of 100 mm / min, the load was increased to 50 N, and the specimen was scratched with a scraper at a distance of 100 mm, and the damaged area was confirmed using a confocal microscope.

[0119]

[0120] Compared to the above visual evaluation of scratch resistance, when scratched with a load of 50 N, which is about 10 times more, Example 20 was damaged to a width of 861.063 um and an area of ​​8643.520 um (see Fig. 2), while Comparative Example 1 was damaged to a width of 884.931 um and an area of ​​13438.266 um, showing that the damage was very large (see Fig. 3). Compared to Comparative Example 1, the scratch resistance of Example 20 was significantly superior.

[0121]

[0122] As shown in Tables 1 to 3 below, it was confirmed that the examples according to the present invention, in particular, had superior self-healing performance, scratch resistance, and mechanical properties compared to the comparative examples by using two or more types of metals.

[0123]

[0124]

[0125]

[0126] As described above, although the present invention has been described by limited embodiments, the present invention is not limited thereto, and it is obvious that various modifications and variations are possible within the scope of the technical idea of ​​the present invention and the equivalent scope of the patent claims to be described below by a person having ordinary skill in the art to which the present invention pertains.

Claims

1. A continuous phase comprising an ionomer composition; and A thermoplastic resin composition having self-healing properties comprising a dispersed phase including a rubber composition, The above ionomer composition comprises ethylene functionalized with a first polar group and a first neutralizing metal, wherein the first neutralizing metal comprises at least one monovalent metal ion and at least one divalent metal ion, A thermoplastic resin composition having self-healing properties, wherein the rubber composition comprises an unsaturated rubber functionalized with a second polar group and a second neutralizing metal, wherein the second neutralizing metal comprises at least one monovalent metal ion and at least one divalent metal ion.

2. In paragraph 1, The above first neutralizing metal comprises at least two or more metals selected from lithium, sodium, potassium, magnesium, calcium and zinc, A thermoplastic resin composition having self-healing properties, wherein the second neutralizing metal comprises at least two or more metals selected from lithium, sodium, potassium, magnesium, calcium and zinc.

3. In paragraph 2, The above first neutralizing metal comprises two or more metals selected from sodium, magnesium and zinc metals, A thermoplastic resin composition having self-healing properties, wherein the second neutralizing metal comprises two or more metals selected from sodium, magnesium and zinc metals.

4. In paragraph 3, A thermoplastic resin composition having self-healing properties, wherein each of the first neutralizing metal and the second neutralizing metal contains sodium and zinc in a ratio of 9:1 to 1:

9.

5. In paragraph 3, A thermoplastic resin composition having self-healing properties, wherein each of the first neutralizing metal and the second neutralizing metal contains sodium and magnesium in a ratio of 9:1 to 1:

9.

6. In paragraph 1, A thermoplastic resin composition having self-healing properties, wherein the first and second neutralizing metals comprise the same type of metal.

7. In paragraph 1, 20 to 95 parts by weight of the above continuous phase; and A thermoplastic resin composition having self-healing properties, comprising 80 to 5 parts by weight of the above dispersed phase.

8. In paragraph 1, The above ionomer composition, A thermoplastic resin composition having self-healing properties, prepared by mixing 1 to 30 parts by weight of a first polar group and 1 to 30 parts by weight of a first neutralizing metal with respect to 100 parts by weight of ethylene.

9. In paragraph 1, The above rubber composition A thermoplastic resin composition having self-healing properties, prepared by mixing 1 to 20 parts by weight of a second polar group and 1 to 20 parts by weight of a second neutralizing metal with respect to 100 parts by weight of unsaturated rubber.

10. In paragraph 1, A thermoplastic resin composition having self-healing properties, wherein the ionomer composition and the rubber composition each contain at least one selected from an initiator, a crosslinking agent, an antioxidant, a lubricant, a catalyst, and a UV stabilizer.

11. In paragraph 1, A thermoplastic resin composition having self-healing properties, wherein the unsaturated rubber is at least one selected from the group consisting of polyisoprene rubber, polybutadiene rubber, ethylene propylene diene EPDM rubber, styrene butadiene rubber, and acrylonitrile butadiene rubber.

12. In paragraph 8 or 9, A thermoplastic resin composition having self-healing properties, wherein the first polar group and the second polar group are each independently selected from the group consisting of acrylic acid, methacrylic acid, carboxylic acid, and polycarboxylic acid containing two or more COOH carboxyl groups.

13. In paragraph 12, A thermoplastic resin composition having self-healing properties, wherein the polycarboxylic acid containing two or more COOH carboxyl groups is selected from the group consisting of malonic acid, succinic acid, glutaric acid, pimelic acid, itaconic acid, and adipic acid.

14. A molded article manufactured from a thermoplastic resin composition having self-healing properties according to any one of claims 1 to 11.

15. In paragraph 14, A molded product, wherein the molded product is selected from automotive interior and exterior materials, electronic products, leisure products, and golf balls.

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