Resin composition, modifier, and composition containing the modifier

Abstract

To provide a resin composition which is usable as a modifier that solves brittleness of a plastic material containing a plurality of resins like a laminate of dissimilar materials that are recycled and recovered, and can improve impact resistance and breaking elongation.SOLUTION: A resin composition (A) contains the following components (1) and (2). (1) Ethylene-acrylic acid copolymer or ethylene-methacrylic acid copolymer having a content of an acrylic acid or a methacrylic acid of 4 mol% or less (a1), and (2) ethylene-acrylic acid copolymer or ethylene-methacrylic acid copolymer having a content of an acrylic acid or a methacrylic acid of 4 mol% or more (a2).SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to the resin composition and a molded article formed of the composition. Background Art

[0002] In recent years, there has been growing concern over environmental pollution caused by plastics, and material recycling of plastic products has been promoted. In material recycling of plastics, the recovered plastic waste is often melted and processed back into raw material pellets, or recycled into consumable materials such as pallets. In this case, if recycling is performed with different types of plastics mixed in the recovered plastic waste, poor mutual compatibility leads to the problem of deteriorated physical properties of the recycled plastic. For this reason, the current process involves sorting the recovered plastic waste by material before recycling it into products.

[0003] However, in the case of multilayer films, multilayer containers and the like formed by laminating different types of plastics, it is difficult to separate the plastics by material, so they cannot be recycled, and the current situation is that they are disposed of in landfills or by incineration.

[0004] Against this backdrop, the addition of compatibilizers is being considered as a means of recycling laminated composite resins. For example, studies have been conducted on the composite recycling of polyethylene (PE)-polyethylene terephthalate (hereinafter sometimes abbreviated as PET) and polypropylene (hereinafter sometimes abbreviated as PP)-ABS using ionomer resin as a compatibilizer (see, for example, Patent Document 1). Furthermore, studies have been conducted on the composite recycling of PE-PET, etc., using oxazoline-based compatibilizers (see, for example, Patent Document 2). In addition, studies have been conducted on the composite recycling of PE-ethylene vinyl alcohol copolymer (hereinafter sometimes abbreviated as EVOH) (see, for example, Patent Document 3). According to these documents, it has been shown that the physical properties of composites such as PE, PET, and EVOH can be improved by adding a compatibilizer. However, the mechanical properties of the recycled resins obtained by these methods are not sufficient, so the development of technologies that can further improve mechanical properties is necessary. Moreover, problems such as increased viscosity, yellowing, and odor have resulted in poor recyclability and limitations on the uses of recycled resins. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Japanese Patent Publication No. 2001-220473 [Patent Document 2] Japanese Patent Publication No. 2004-182957 [Patent Document 3] Special Publication No. 2009-535452 [Overview of the project] [Problems that the invention aims to solve]

[0006] The present invention has been made in view of the above problems, and its objective is to provide a resin composition that can be used as a modifier capable of overcoming the brittleness of plastic materials containing multiple resins, such as laminates of dissimilar materials recovered through recycling, and improving their impact resistance and elongation at break. [Means for solving the problem]

[0007] As a result of diligent research to solve the above problems, the present inventors have found that a resin composition containing an ethylene-acrylic acid copolymer with an acrylic acid content of 4 mol% or less, or an ethylene-methacrylic acid copolymer with a methacrylic acid content of 4 mol% or less, and an ethylene-acrylic acid copolymer with an acrylic acid content of more than 4 mol%, or an ethylene-methacrylic acid copolymer with a methacrylic acid content of more than 4 mol%, can be suitably used as a resin modifier that can improve the impact resistance and elongation at break of brittle materials composed of multiple resin components, and have completed the present invention.

[0008] Each aspect of the present invention is shown below [1] to

[14] . [1] A resin composition (A) comprising the following components (1) and (2). (1) Ethylene-acrylic acid copolymer with an acrylic acid content of 4 mol% or less, or ethylene-methacrylic acid copolymer with a methacrylic acid content of 4 mol% or less (a1) (2) Ethylene-acrylic acid copolymer having an acrylic acid content greater than 4 mol%, or ethylene-methacrylic acid copolymer having a methacrylic acid content greater than 4 mol% (a2) [2] The resin composition (A) according to [1], further comprising an ethylene-acrylic acid copolymer or an ethylene-methacrylic acid copolymer having a different acrylic acid or methacrylic acid content than that of (1) and (2). [3] The resin composition (A) according to [1] or [2] above, wherein the difference in the acrylic acid or methacrylic acid content between (1) and (2) is 1 mol% or more and 6.5 mol% or less. [4] A resin composition (A) according to any one of [1] to [3] above, comprising a crosslinking agent (a3). [5] A modifier comprising the resin composition (A) described in any of [1] to [4] above. [6] A resin composition comprising 1% by weight or more and 50% by weight or less of the resin composition (A) described in any of [1] to [4] above, and 50% by weight or more and 99% by weight or less of the thermoplastic resin (B) (where the total of (B) and (A) is 100% by weight). [7] The resin composition according to [6] above, wherein the thermoplastic resin (B) is at least one selected from the group consisting of polyolefin resins, acrylic acid resins, polyamide resins, polyester resins, polycarbonate resins, polystyrene resins, and styrene-acrylonitrile copolymers. [8] The resin composition according to [6] above, wherein the thermoplastic resin (B) is at least one selected from the group consisting of high-density polyethylene, low-density polyethylene, linear low-density polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-vinyl alcohol copolymer, nylon 6, nylon 6,6, nylon 11, nylon 12, polyethylene terephthalate, glycol-modified polyethylene terephthalate resin, polybutylene terephthalate, polylactic acid (including poly-L-lactic acid, poly-D-lactic acid, copolymer of L-lactic acid and D-lactic acid, stereocomplex of poly-L-lactic acid and poly-D-lactic acid), and polybutylene succinate. [9] The resin composition according to [6] above, wherein the thermoplastic resin (B) comprises at least one selected from the group consisting of high-density polyethylene, low-density polyethylene, linear low-density polyethylene, polypropylene, and ethylene-propylene copolymer, and at least one selected from the group consisting of ethylene-vinyl alcohol copolymer, nylon 6, nylon 6,6, nylon 11, nylon 12, polyethylene terephthalate, glycol-modified polyethylene terephthalate resin, and polybutylene terephthalate.

[10] The resin composition according to any one of [6] to [9] above, wherein the thermoplastic resin (B) is two or more types of resin.

[11] The resin composition according to any one of [6] to

[10] above, wherein the thermoplastic resin (B) is a used molded article.

[12] A method for producing a resin composition according to any one of [6] to

[11] above, comprising a kneading step of kneading a thermoplastic resin (B) and the modifier described in [5] above using a twin-screw extruder.

[13] A method for producing the resin composition according to

[12] above, wherein the kneading step is performed under the condition that the screw rotation speed of the twin-screw extruder is 50 rpm or more and 3000 rpm or less.

[14] A molded article obtained by molding any of the resin compositions described in [6] to

[11] above. [Effects of the Invention]

[0009] According to the present invention, it is possible to provide a resin composition that exhibits excellent effects in modifying impact resistance and elongation at break, and is useful as a modifier for resin molded products that require these physical properties. In particular, by using this resin composition, it is possible to effectively recycle plastic waste containing multiple resins. [Modes for carrying out the invention]

[0010] The present invention will be described in detail below with reference to its preferred embodiments.

[0011] A resin composition (A) according to one aspect of the present invention comprises an ethylene-acrylic acid copolymer (a1) having an acrylic acid content of 4 mol% or less, or an ethylene-methacrylic acid copolymer (a1) having a methacrylic acid content of 4 mol% or less (hereinafter referred to as "polymer (a1)"), and an ethylene-acrylic acid copolymer (a2) having an acrylic acid content greater than 4 mol%, or an ethylene-methacrylic acid copolymer (a2) having a methacrylic acid content greater than 4 mol% (hereinafter referred to as "polymer (a2)").

[0012] Ethylene-acrylic acid copolymers (hereinafter sometimes abbreviated as EAA) can be conveniently selected from commercially available products, and are sold by SK Global Chemical under the trade name Primacol and by Honeywell under the trade name AC.

[0013] An ethylene-methacrylic acid copolymer (hereinafter sometimes abbreviated as EMAA) can be conveniently selected from commercial products, and is sold under the trade name Nucrel by Mitsui-Dow Polychemical Co., Ltd.

[0014] In the copolymer (a1), the acrylic acid content of the ethylene-acrylic acid copolymer or the methacrylic acid content of the ethylene-methacrylic acid copolymer is 4 mol% or less. This improves compatibility with polyolefins in the thermoplastic resin (B).

[0015] In the copolymer (a2), the acrylic acid content of the ethylene-acrylic acid copolymer or the methacrylic acid content of the ethylene-methacrylic acid copolymer is greater than 4 mol%, preferably 6 mol% or more, and more preferably 8 mol% or more. This improves compatibility with highly polar components such as polyester and polyamide (hereinafter sometimes abbreviated as PA) in the thermoplastic resin (B).

[0016] It is preferable that the resin composition (A) further comprises an ethylene-acrylic acid copolymer or an ethylene-methacrylic acid copolymer having an acrylic acid or methacrylic acid content different from those of (1) and (2) above.

[0017] In the resin composition (A), all the content differences between each acrylic acid or methacrylic acid are preferably 0.1 mol% or more, and more preferably 0.5 mol% or more. Thereby, when the resin composition (A) is blended as a modifier into the thermoplastic resin (B), the compatibility is further improved, and the impact resistance and elongation at break of the obtained composition are improved.

[0018] Further, the difference in acrylic acid or methacrylic acid content between the copolymer (a1) and the copolymer (a2) is preferably 1 mol% or more and 6.5 mol% or less, more preferably 1 mol% or more and 5.5 mol% or less. Thereby, when the resin composition (A) is blended as a modifier into the thermoplastic resin (B), the compatibility is further improved, and the impact resistance and elongation at break of the obtained composition are improved.

[0019] In the resin composition (A), the mixing ratio of the copolymer (a1) and the copolymer (a2) is preferably 50% by weight or more and 99% by weight or less of the copolymer (a1) and 1% by weight or more and 50% by weight or less of the copolymer (a2), where the total of (a1) and (a2) is 100% by weight, and more preferably 60% by weight or more and 90% by weight or less of the copolymer (a1) and 10% by weight or more and 40% by weight or less of the copolymer (a2), where the total of (a1) and (a2) is 100% by weight. This further improves the compatibility and impact resistance of the blended resin.

[0020] In the resin composition (A), crosslinking modification treatment of (a1) and (a2) may be performed. Examples of the crosslinking modification treatment include a method of adding a crosslinking agent to the resin composition (A) and performing melt kneading treatment, and a method by electron beam irradiation, and a crosslinked modified product treated by the melt kneading method is preferred. When the melt kneading method is used, it is preferable to include a crosslinking agent (a3). Examples of the crosslinking agent (a3) include epoxy compounds, organic peroxides, polyfunctional isocyanate compounds, aziridine group-containing compounds, carbodiimides, oxazolines, and amino resins. Among these, epoxy compounds and organic peroxides are preferably used from the viewpoint of reactivity.

[0021] There is no particular limitation as long as it is an epoxy compound or an organic peroxide. For example, there is no particular limitation for an epoxy compound as long as it is a compound having at least one epoxy group. Examples of the epoxy compound include bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, novolac glycidyl ether, and glycerin polyglycidyl ether.

[0022] Examples of organic peroxides include dicumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, 1,1-di(t-butylperoxy)cyclohexane, 2,5-dimethyl-2,5-di(t-butylperoxy)hexine-3, 1,3-bis(t-butylperoxyisopropyl)benzene, 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, 1,3-di-(t-butylperoxy)-diisopropylbenzene, n-butyl-4,4-bis(t-butylperoxy)valerate, benzoyl peroxide, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, t-butylperoxybenzoate, t-butylperoxyisopropyl carbonate, diacetyl peroxide, lauroyl peroxide, and t-butylcumyl peroxide.

[0023] These can be used individually or in combination of two or more types, and it is preferable to adjust the amount of crosslinking agent (a3) ​​added to 100 parts of resin composition (A) in the range of 0.001 to 10 parts.

[0024] One embodiment of the present invention is a modifier comprising a resin composition (A).

[0025] The thermoplastic resin composition (B) containing the modifier is preferably at least one selected from the group consisting of polyolefin resins, acrylic acid resins, polyamide resins, polyester resins, polycarbonate resins, polystyrene resins, and styrene-acrylonitrile copolymers, and more preferably at least two, due to their excellent compatibility with the modifier.

[0026] Examples of polyolefin resins include high-density polyethylene, low-density polyethylene, linear low-density polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-vinyl alcohol copolymer, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, polybutadiene, and polyisoprene.

[0027] Examples of acrylic acid-based resins include polyacrylic acid, methyl polyacrylate, ethyl polyacrylate, butyl polyacrylate, octyl polyacrylate, polymethacrylic acid, polymethyl polymethacrylate, polyethyl polymethacrylate, polybutyl polymethacrylate, and polyoctyl polymethacrylate.

[0028] Examples of polyamide resins include nylon 6, nylon 6,6, nylon 11, and nylon 12.

[0029] Examples of polyester resins include polyethylene terephthalate, glycol-modified polyethylene terephthalate resin (PETG resin), polybutylene terephthalate, polylactic acid (including poly-L-lactic acid, poly-D-lactic acid, copolymers of L-lactic acid and D-lactic acid, and stereocomplexes of poly-L-lactic acid and poly-D-lactic acid), polybutylene succinate, poly(butylene succinate / adipate), polyethylene succinate, poly(butylene succinate / terephthalate), poly(butylene adipate / terephthalate), poly(hydroxybutyrate / hydroxyhexanoate), polyglycolic acid, poly-3-hydroxybutyrate, and polycaprolactone.

[0030] Among these, at least one thermoplastic resin selected from the group consisting of high-density polyethylene, low-density polyethylene, linear low-density polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-vinyl alcohol copolymer, nylon 6, nylon 6,6, nylon 11, nylon 12, polyethylene terephthalate, glycol-modified polyethylene terephthalate resin (PETG resin), polybutylene terephthalate, polylactic acid (including poly-L-lactic acid, poly-D-lactic acid, copolymer of L-lactic acid and D-lactic acid, and stereocomplex of poly-L-lactic acid and poly-D-lactic acid) and polybutylene succinate is preferred as the thermoplastic resin constituting the thermoplastic resin (B) because it shows significant improvement in impact resistance and elongation at break when blended with resin composition (A).

[0031] More preferably, the material comprises at least one selected from the group consisting of high-density polyethylene, low-density polyethylene, linear low-density polyethylene, polypropylene, and ethylene-propylene copolymer, and at least one selected from the group consisting of ethylene-vinyl alcohol copolymer, nylon 6, nylon 6,6, nylon 11, nylon 12, polyethylene terephthalate, glycol-modified polyethylene terephthalate resin, and polybutylene terephthalate. The thermoplastic resin (B) may be unused virgin resin or resin obtained by recovering used molded articles. That is, this includes forms in which all of one or more types of resin are unused resins, forms in which at least one of the one or more types of resin is a used resin, and forms in which all of the one or more types of resin are used resins.

[0032] Thermoplastic resin (B) may contain multiple types of resin when using resin obtained from recovered used molded products. In this case, it may contain organic impurities such as PVC resin, wax, adhesive, plasticizer, and antioxidant. On the other hand, it may also contain inorganic impurities such as fillers.

[0033] The mixing ratio of resin composition (A) and thermoplastic resin (B) is preferably such that thermoplastic resin (B) is 50% to 99% by weight and resin composition (A) is 1% to 50% by weight. A resin composition obtained by including 99% or less of thermoplastic resin (B) will have excellent impact resistance. On the other hand, a resin composition obtained by including 50% or more of thermoplastic resin (B) will have excellent rigidity. More preferably, the mixture contains 60% to 95% by weight of thermoplastic resin (B) and 5% to 40% by weight of resin composition (A), and even more preferably, 70% to 95% by weight of thermoplastic resin (B) and 5% to 30% by weight of resin composition (A).

[0034] When a modifier containing a resin composition (A) is incorporated into a thermoplastic resin (B), it can be manufactured by a manufacturing method that includes a kneading step of kneading the modifier and the thermoplastic resin (B).

[0035] The mixing method includes simultaneously mixing the modifier and the various materials constituting the thermoplastic resin (B) in a mixing device, and pre-mixing only the modifier, then blending the modified modifier with the thermoplastic resin (B) and further mixing. The latter method is preferable because it allows the modifier to mix more uniformly, resulting in a stable acquisition of the desired physical properties.

[0036] As long as the mixing equipment can uniformly disperse each component, there are no particular restrictions, and it can be manufactured using commonly used resin mixing equipment. Examples of mixing equipment include single-screw extruders, twin-screw extruders, multi-screw extruders, Banbury mixers, pressure kneaders, rotary rolls, and internal mixers. Among these, twin-screw extruders are more preferred due to their superior dispersibility and continuous production capabilities.

[0037] When kneading with a twin-screw extruder, the screw rotation speed is not particularly limited, but it is preferable to knead at 50 rpm to 3000 rpm, and more preferably at 300 rpm to 3000 rpm. A screw rotation speed of 50 rpm or higher is preferable because it improves the dispersibility of each mixed component and results in a resin with excellent physical properties. A screw rotation speed of 3000 rpm or lower is also preferable because it prevents deterioration of the resin due to excessive shear heat, resulting in a resin with excellent physical properties.

[0038] When an extruder is used in the kneading process, the resin composition kneaded in the extruder, preferably the resin composition kneaded under the high-speed shearing conditions of 50 rpm to 3000 rpm, can be used as the raw material. Alternatively, the molded body obtained by extruding it directly in the extruder can be used as the molded product.

[0039] The mixing temperature is preferably around the melting point of the component with the lowest melting point among the thermoplastic resins (B), or the glass transition temperature if it is an amorphous resin, or around 300°C.

[0040] The resin composition (A) and the thermoplastic resin (B) may contain antistatic agents, light stabilizers, ultraviolet absorbers, nucleating agents, lubricants, antioxidants, antiblocking agents, flow improvers, mold release agents, flame retardants, colorants, inorganic neutralizing agents, hydrochloric acid absorbers, filler conductive agents, chain length extenders, hydrolysis inhibitors, etc., to the extent that they do not impair the effects of the present invention.

[0041] If the above resin composition contains components other than resin composition (A) and thermoplastic resin (B), the content of these components can be expressed as the amount added relative to 100 parts by weight of the sum of (A) and (B). In other words, the notation "~by weight%" for (A) and (B) above refers to the ratio of (A) and (B), and the ratios of other components can be defined separately.

[0042] Furthermore, the above resin composition can be used in any form, such as pellets or powder.

[0043] A molded article according to one aspect of the present invention is obtained by molding the above-mentioned resin composition. The molding method for the resin composition is arbitrary and includes, for example, shape extrusion, film, sheet, blow molding, injection molding, foaming, extrusion coating, and rotational molding. The molded article can be used for various applications such as automotive parts, housings for electrical and electronic components, building materials, civil engineering components, agricultural materials, containers, packaging materials, adhesives, and daily necessities. [Examples]

[0044] The present invention will be described below with reference to examples and comparative examples, but the present invention is not limited to these. (1) Meltmas flow rate (MFR) The MFRs of ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, and thermoplastic resin (B) were measured using a melt indexer (manufactured by Takara Kogyo Co., Ltd.) at 190°C and a load of 2.16 kg. (2) Impact strength Impact strength was measured in accordance with JIS P 8134. A press-molded sheet with a thickness of 0.1 mm was tested using a film impact tester (Toyo Seiki, FT-M model) under the conditions of a test volume of 3 J and a hemispherical hammer tip. (3) Tensile test A 0.1 mm thick sheet was press-molded and punched into an ASTM D-1822-L dumbbell-shaped test specimen. The specimen dimensions were 63.5 mm in total length, 9.53 mm in parallel section length, 3.18 mm in parallel section width, 0.1 mm in thickness, and 9.53 mm in gripping section width. The specimen was tested using a Tensilon tensile testing machine (Orientec, RTE-1210) under conditions of a chuck distance of 30 mm and a tensile speed of 200 mm / min. The point at which the specimen fractured was defined as the elongation at fracture (elongation at fracture [%] = tensile length required to fracture [mm] / chuck distance of 30 mm), and the stress at fracture was defined as the fracture stress.

[0045] Example 1 A resin composition (A) with the following composition was used. [Resin composition (A)] • Ethylene-acrylic acid copolymer (a1-1) (manufactured by SK Global Chemical Co., Ltd., product name PRIMACOR1321) 65% by weight, with an acrylic acid content of 2.6 mol% and a melt mass flow rate of 2.6 g / 10 min. • Ethylene-acrylic acid copolymer (a2-1) (manufactured by SK Global Chemical Co., Ltd., product name PRIMACOR5980I) 35% by weight, with an acrylic acid content of 8.9 mol% and a melt mass flow rate of 300 g / 10 min. The above resins were dry-blended and melt-kneaded using a twin-screw extruder with a screw diameter of 25 mm (Technovel product name ULTnano25TW) at a resin temperature of 160°C and a screw rotation speed of 150 rpm to obtain pellets of resin composition (A).

[0046] As the thermoplastic resin (B), a thermoplastic resin composition with the following composition was used. [Composition of thermoplastic resin (B)] • Melt mass flow rate 3g / 10 min, low-density polyethylene (B-1) (manufactured by Tosoh Corporation, product name Petrocene 205) 70% by weight, with a melting point of 111°C. • 30% by weight of ethylene-vinyl alcohol copolymer (B-2) (manufactured by Kuraray Co., Ltd., product name EVAL C109B) with an ethylene content of 35 mol% and a melting point of 177°C. A resin composition was obtained by dry blending 80% by weight of thermoplastic resin (B) composition and 20% by weight of resin composition (A), and melt-kneading the mixture using a twin-screw extruder with a screw diameter of 25 mm (Technovel product name ULTnano25TW) at a resin temperature of 200°C and a screw rotation speed of 300 rpm.

[0047] The obtained resin composition was press-molded using a press molding machine (AWFA-50 model, manufactured by Shinto Metal Industries Co., Ltd.) under the following conditions: pressure of 10 MPa, heating temperature of 200°C (primary pressurization for 3 minutes, secondary pressurization for 3 minutes), and cooling temperature of 25°C (for 4 minutes) to obtain a press sheet with a thickness of 0.1 mm.

[0048] Impact and tensile tests were conducted using the obtained press sheets. The evaluation results are shown in Table 1.

[0049] Example 2 A press sheet was obtained by the same method as in Example 1, except that a resin composition with the following composition was used as resin composition (A). [Resin composition (A)] • Ethylene-acrylic acid copolymer (a1-2) (manufactured by SK Global Chemical Co., Ltd., product name PRIMACOR3540) 65% by weight, with an acrylic acid content of 3.5 mol% and a melt mass flow rate of 7 g / 10 min. • Ethylene-acrylic acid copolymer (a2-1) (manufactured by SK Global Chemical Co., Ltd., product name PRIMACOR5980I) 35% by weight, with an acrylic acid content of 8.9 mol% and a melt mass flow rate of 300 g / 10 min. Impact and tensile tests were conducted using the obtained press sheets. The evaluation results are shown in Table 1.

[0050] Example 3 A press sheet was obtained by the same method as in Example 1, except that a resin composition with the following composition was used as resin composition (A). [Resin composition (A)] • Ethylene-acrylic acid copolymer (a1-1) (manufactured by SK Global Chemical Co., Ltd., product name PRIMACOR1321) 65% by weight, with an acrylic acid content of 2.6 mol% and a melt mass flow rate of 2.6 g / 10 min. • Ethylene-acrylic acid copolymer (a1-2) (manufactured by SK Global Chemical Co., Ltd., product name PRIMACOR3540) 10% by weight, with an acrylic acid content of 3.5 mol% and a melt mass flow rate of 7 g / 10 min. • Ethylene-acrylic acid copolymer (a2-1) (manufactured by SK Global Chemical Co., Ltd., product name PRIMACOR5980I) 25% by weight, with an acrylic acid content of 8.9 mol% and a melt mass flow rate of 300 g / 10 min. Impact and tensile tests were conducted using the obtained press sheets. The evaluation results are shown in Table 1.

[0051] Example 4 A thermoplastic resin composition with the following composition was used as the thermoplastic resin (B). [Composition of thermoplastic resin (B)] • Melt mass flow rate 3g / 10 min, low-density polyethylene (B-1) (manufactured by Tosoh Corporation, product name Petrocene 205) 70% by weight, with a melting point of 111°C. • Nylon 6 (B-3) (manufactured by Ube Industries, Ltd., product name UBE Nylon 1022D) 30% by weight, with a melting point of 220°C. 80% by weight of thermoplastic resin composition (B) and 20% by weight of resin composition (A) described in Example 1 were dry blended, and the mixture was melt-kneaded using a twin-screw extruder with a screw diameter of 25 mm (Technovel product name ULTnano25TW) at a resin temperature of 230°C and a screw rotation speed of 300 rpm to obtain the resin composition.

[0052] The obtained resin composition was press-molded using a press molding machine (AWFA-50 model, manufactured by Shinto Metal Industries Co., Ltd.) under the following conditions: pressure of 10 MPa, heating temperature of 230°C (primary pressurization for 3 minutes, secondary pressurization for 3 minutes), and cooling temperature of 25°C (for 4 minutes) to obtain a press sheet with a thickness of 0.1 mm.

[0053] Impact and tensile tests were conducted using the obtained press sheets. The evaluation results are shown in Table 1.

[0054] Example 5 A thermoplastic resin composition with the following composition was used as the thermoplastic resin (B). [Composition of thermoplastic resin (B)] • Melt mass flow rate 3g / 10 min, low-density polyethylene (B-1) (manufactured by Tosoh Corporation, product name Petrocene 205) 70% by weight, with a melting point of 111°C. • 30% by weight of polyethylene terephthalate (B-4) (manufactured by Unitika Ltd., MA-2103), which has a melting point of 255°C. 80% by weight of thermoplastic resin composition (B) and 20% by weight of resin composition (A) described in Example 1 were dry blended, and the mixture was melt-kneaded using a twin-screw extruder with a screw diameter of 25 mm (Technovel product name ULTnano25TW) at a resin temperature of 270°C and a screw rotation speed of 150 rpm to obtain the resin composition.

[0055] The obtained resin composition was press-molded using a press molding machine (AWFA-50 model, manufactured by Shinto Metal Industries Co., Ltd.) under the following conditions: pressure of 10 MPa, heating temperature of 230°C (primary pressurization for 3 minutes, secondary pressurization for 3 minutes), and cooling temperature of 25°C (for 4 minutes) to obtain a press sheet with a thickness of 0.1 mm.

[0056] Impact and tensile tests were conducted using the obtained press sheets. The evaluation results are shown in Table 1.

[0057] Comparative Example 1 A press sheet was obtained using the same method as in Example 1, except that only the composition of the thermoplastic resin (B) described below was used. [Composition of thermoplastic resin (B)] • Melt mass flow rate 3g / 10 min, low-density polyethylene (B-1) (manufactured by Tosoh Corporation, product name Petrocene 205) 70% by weight, with a melting point of 111°C. • 30% by weight of ethylene-vinyl alcohol copolymer (B-2) (manufactured by Kuraray Co., Ltd., product name EVAL C109B) with an ethylene content of 35 mol% and a melting point of 177°C. Impact and tensile tests were conducted using the obtained press sheets. The evaluation results are shown in Table 1.

[0058] Comparative Example 2 A press sheet was obtained using the same method as in Example 5, except that only the composition of the thermoplastic resin (B) described below was used. [Composition of thermoplastic resin (B)] • Melt mass flow rate 3g / 10 min, low-density polyethylene (B-1) (manufactured by Tosoh Corporation, product name Petrocene 205) 70% by weight, with a melting point of 111°C. • 30% by weight of polyethylene terephthalate (B-4) (manufactured by Unitika Ltd., MA-2103), which has a melting point of 255°C. Impact and tensile tests were conducted using the obtained press sheets. The evaluation results are shown in Table 1.

[0059] [Table 1]

[0060] Example 6 A press sheet was obtained by the same method as in Example 5, except that a thermoplastic resin composition with the following composition was used as the thermoplastic resin (B). [Composition of thermoplastic resin (B)] • Melt mass flow rate 3g / 10 min, low-density polyethylene (B-1) (manufactured by Tosoh Corporation, product name Petrocene 205) 70% by weight, with a melting point of 111°C. • 10% by weight of ethylene-vinyl alcohol copolymer (B-2) (manufactured by Kuraray Co., Ltd., product name EVAL C109B) with an ethylene content of 35 mol% and a melting point of 177°C. • Nylon 6 (B-3) (manufactured by Ube Industries, Ltd., product name UBE Nylon 1022D) 10% by weight, with a melting point of 220°C. • 10% by weight of polyethylene terephthalate (B-4) (manufactured by Unitika Ltd., MA-2103), with a melting point of 255°C. Impact and tensile tests were conducted using the obtained press sheets. The evaluation results are shown in Table 2.

[0061] Example 7 A press sheet was obtained by the same method as in Example 6, except that the thermoplastic resin (B) was 65% by weight and the resin composition (A) was 35% by weight.

[0062] Impact and tensile tests were conducted using the obtained press sheets. The evaluation results are shown in Table 2.

[0063] Example 8 A press sheet was obtained by the same method as in Example 6, except that a resin composition with the following composition was used as resin composition (A). [Composition of resin composition (A)] • Ethylene-acrylic acid copolymer (a1-1) (manufactured by SK Global Chemical Co., Ltd., product name PRIMACOR1321) 65% by weight, with an acrylic acid content of 2.6 mol% and a melt mass flow rate of 2.6 g / 10 min. • Ethylene-methacrylic acid copolymer (a1-3) (manufactured by Mitsui Dow Polychemical Co., Ltd., product name Nucrel N1108C) 10% by weight, with a methacrylic acid content of 3.9 mol% and a melt mass flow rate of 8 g / 10 min. • Ethylene-acrylic acid copolymer (a2-1) (manufactured by SK Global Chemical Co., Ltd., product name PRIMACOR5980I) 25% by weight, with an acrylic acid content of 8.9 mol% and a melt mass flow rate of 300 g / 10 min. Impact and tensile tests were conducted using the obtained press sheets. The evaluation results are shown in Table 2.

[0064] Example 9 A press sheet was obtained by the same method as in Example 6, except that a resin composition with the following composition was used as resin composition (A). [Composition of resin composition (A)] • Ethylene-acrylic acid copolymer (a1-1) (manufactured by SK Global Chemical Co., Ltd., product name PRIMACOR1321) 45% by weight, with an acrylic acid content of 2.6 mol% and a melt mass flow rate of 2.6 g / 10 min. • Ethylene-acrylic acid copolymer (a1-2) (manufactured by SK Global Chemical Co., Ltd., product name PRIMACOR3540) 30% by weight, with an acrylic acid content of 3.5 mol% and a melt mass flow rate of 7 g / 10 min. • Ethylene-acrylic acid copolymer (a2-1) (manufactured by SK Global Chemical Co., Ltd., product name PRIMACOR5980I) 25% by weight, with an acrylic acid content of 8.9 mol% and a melt mass flow rate of 300 g / 10 min. Impact and tensile tests were conducted using the obtained press sheets. The evaluation results are shown in Table 2.

[0065] Example 10 A press sheet was obtained by the same method as in Example 3, except that a resin composition with the following composition was used as resin composition (A). [Composition of resin composition (A)] • Ethylene-acrylic acid copolymer (a1-1) (manufactured by SK Global Chemical Co., Ltd., product name PRIMACOR1321) 65% by weight, with an acrylic acid content of 2.6 mol% and a melt mass flow rate of 2.6 g / 10 min. • Ethylene-acrylic acid copolymer (a1-2) (manufactured by SK Global Chemical Co., Ltd., product name PRIMACOR3540) 10% by weight, with an acrylic acid content of 3.5 mol% and a melt mass flow rate of 7 g / 10 min. • Ethylene-acrylic acid copolymer (a2-1) (manufactured by SK Global Chemical Co., Ltd., product name PRIMACOR5980I) 25% by weight, with an acrylic acid content of 8.9 mol% and a melt mass flow rate of 300 g / 10 min. • 0.5 parts of bisphenol A glycidyl ether (D3415, manufactured by Sigma-Aldrich) Impact and tensile tests were conducted using the obtained press sheets. The evaluation results are shown in Table 2. Comparative Example 3 A press sheet was obtained using the same method as in Example 6, except that only the composition of the thermoplastic resin (B) described below was used. [Composition of thermoplastic resin (B)] • Melt mass flow rate 3g / 10 min, low-density polyethylene (B-1) (manufactured by Tosoh Corporation, product name Petrocene 205) 70% by weight, with a melting point of 111°C. • 10% by weight of ethylene-vinyl alcohol copolymer (B-2) (manufactured by Kuraray Co., Ltd., product name EVAL C109B) with an ethylene content of 35 mol% and a melting point of 177°C. • Nylon 6 (B-3) (manufactured by Ube Industries, Ltd., product name UBE Nylon 1022D) 10% by weight, with a melting point of 220°C. • 10% by weight of polyethylene terephthalate (B-4) (manufactured by Unitika Ltd., MA-2103), with a melting point of 255°C. Impact and tensile tests were conducted using the obtained press sheets. The evaluation results are shown in Table 2.

[0066] Comparative Example 4 A press sheet was obtained by the same method as in Example 6, except that a resin composition with the following composition was used as resin composition (A). [Composition of resin composition (A)] • Ethylene-acrylic acid copolymer (a1-1) (manufactured by SK Global Chemical Co., Ltd., product name PRIMACOR1321) 100% by weight, with an acrylic acid content of 2.6 mol% and a melt mass flow rate of 2.6 g / 10 min. Impact and tensile tests were conducted using the obtained press sheets. The evaluation results are shown in Table 2.

[0067] Comparative Example 5 A press sheet was obtained by the same method as in Example 6, except that a resin composition with the following composition was used as resin composition (A). [Composition of resin composition (A)] • Ethylene-acrylic acid copolymer (a1-1) (manufactured by SK Global Chemical Co., Ltd., product name PRIMACOR1321) 65% by weight, with an acrylic acid content of 2.6 mol% and a melt mass flow rate of 2.6 g / 10 min. • Ethylene-acrylic acid copolymer (a1-2) (manufactured by SK Global Chemical Co., Ltd., product name PRIMACOR3540) 35% by weight, with an acrylic acid content of 3.5 mol% and a melt mass flow rate of 7 g / 10 min. Impact and tensile tests were conducted using the obtained press sheets. The evaluation results are shown in Table 2.

[0068] Comparative Example 6 A press sheet was obtained by the same method as in Example 6, except that the thermoplastic resin (B) was 40% by weight and the resin composition (A) was 60% by weight.

[0069] Impact and tensile tests were conducted using the obtained press sheets. The evaluation results are shown in Table 2.

[0070] [Table 2] [Industrial applicability]

[0071] Molded articles made from the resin composition of the present invention can be used in a variety of applications, including automotive parts, housings for electrical and electronic components, building materials, civil engineering materials, agricultural materials, containers, packaging materials, adhesives, and daily necessities.

Claims

1. A plastic material modifier containing multiple recycled resins, comprising a resin composition (A) containing 50% to 99% by weight of component (1) and 1% to 50% by weight of component (2) (provided that the total of (1) and (2) is 100% by weight). (1) Ethylene-acrylic acid copolymer with an acrylic acid content of 4 mol% or less, or metha Ethylene-methacrylic acid copolymer (a1) with a lylic acid content of 4 mol% or less (2) Ethylene-acrylic acid copolymer having an acrylic acid content greater than 4 mol%, or Ethylene-methacrylic acid copolymer (a2) with a tacrylic acid content greater than 4 mol%

2. The modifier according to claim 1, wherein the resin composition (A) further comprises an ethylene-acrylic acid copolymer or an ethylene-methacrylic acid copolymer having an acrylic acid or methacrylic acid content different from that of (1) and (2) above.

3. The modifier according to claim 1 or 2, wherein the resin composition (A) has a difference in the content of acrylic acid or methacrylic acid between (1) and (2) above of 1 mol% or more and 6.5 mol% or less.

4. A modifier according to any one of claims 1 to 3, wherein the resin composition (A) comprises a crosslinking agent (a3).

5. A resin composition comprising 1% by weight or more and 50% by weight or less of the modifier described in any one of claims 1 to 4, and 50% by weight or more and 99% by weight or less of the thermoplastic resin (B) (where the total of (B) and (A) is 100% by weight).

6. Thermoplastic resin (B) is polyolefin resin, acrylic acid resin, polyamide resin, Polyester resins, polycarbonate resins, polystyrene resins and styrene-acrylo The resin according to claim 5, which is at least one selected from the group consisting of nitrile copolymers. composition.

7. Thermoplastic resin (B) is high-density polyethylene, low-density polyethylene, linear low-density polyethylene Teylene, polypropylene, ethylene-propylene copolymer, ethylene-vinyl alcohol Copolymer, nylon 6, nylon 6,6, nylon 11, nylon 12, polyethylene Rephthalate, glycol-modified polyethylene terephthalate resin, polybutylene terephthalate Rate, polylactic acid (poly-L-lactic acid, poly-D-lactic acid, copolymer of L-lactic acid and D-lactic acid), (Containing a stereocomplex of poly-L-lactic acid and poly-D-lactic acid) and polybutylene succinate The resin composition according to claim 5, wherein it is at least one selected from the group consisting of nates.

8. Thermoplastic resin (B) is high-density polyethylene, low-density polyethylene, linear low-density polyethylene A small number selected from the group consisting of ethylene, polypropylene, and ethylene-propylene copolymer. Both are 1 type, ethylene-vinyl alcohol copolymer, nylon 6, nylon 6,6, and nylon Nylon 11, Nylon 12, Polyethylene terephthalate, Glycol-modified polyethylene At least one selected from the group consisting of reflatate resin and polybutylene terephthalate The resin composition according to claim 5, comprising each of the seeds.

9. The resin composition according to claim 5, wherein the thermoplastic resin (B) is two or more types of resins.

10. Thermoplastic resin (B) is polyolefin resin, acrylic acid resin, polyamide resin, Polyester resins, polycarbonate resins, polystyrene resins and styrene-acrylo The resin according to claim 5, which is two or more selected from the group consisting of nitrile copolymers. composition.

11. Thermoplastic resin (B) is high-density polyethylene, low-density polyethylene, linear low-density polyethylene Teylene, polypropylene, ethylene-propylene copolymer, ethylene-vinyl alcohol Copolymer, nylon 6, nylon 6,6, nylon 11, nylon 12, polyethylene Rephthalate, glycol-modified polyethylene terephthalate resin, polybutylene terephthalate Rate, polylactic acid (poly-L-lactic acid, poly-D-lactic acid, copolymer of L-lactic acid and D-lactic acid), (Containing a stereocomplex of poly-L-lactic acid and poly-D-lactic acid) and polybutylene succinate The resin composition according to claim 5, comprising two or more types selected from the group consisting of nates.

12. The resin composition according to any one of claims 5 to 11, wherein the thermoplastic resin (B) is a resin obtained by recovering a used molded article.

13. A method for producing a resin composition according to any one of claims 5 to 12, comprising a kneading step of kneading a thermoplastic resin (B) and a modifier according to any one of claims 1 to 4 in a twin-screw extruder.

14. The mixing process is performed under the condition that the screw rotation speed of the twin-screw extruder is between 50 rpm and 3000 rpm. A method for producing the resin composition according to claim 13.

15. A molded article obtained by molding the resin composition according to any one of claims 5 to 12.

Images