Resin composition and molded article using the resin composition

Abstract

To provide a resin composition which is excellent in impact resistance, flexibility and recyclability by blending a specific ethylene-vinyl acetate copolymer composition in a composite resin where a fragile resin, a recycled resin or two or more different resins are mixed, and to provide a molding using the resin composition.SOLUTION: A resin composition contains 1 wt.% or more and 99 wt.% or less of a thermoplastic resin (A), and 1 wt.% or more and 99 wt.% or less of an ethylene-vinyl acetate copolymer composition (B) containing two or more kinds of ethylene-vinyl acetate copolymers having different vinyl acetate contents (where the total of the (A) and the (B) is 100 wt.%).SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a thermoplastic resin (A) and two or more ethylene-acetate copolymers having different vinyl acetate contents. and a composition (B) of ethylene-vinyl acetate copolymer containing a vinyl acetate copolymer, The present invention relates to a resin composition having excellent elongation at break and to a molded article made from the composition. [Background technology]

[0002] Polyester and amorphous polymers are used in electronic device casings and automobiles, taking advantage of their high rigidity and durability. From industrial components that require high mechanical strength, such as automotive materials, to consumables such as food packaging and daily necessities In recent years, there has been growing social interest in environmental issues, and efforts are being made to reduce the environmental impact. It is desirable to develop new materials, especially biomass-derived resins, and to develop technologies for recycling resins. It is being done.

[0003] However, when used in conventional applications, further improvements in mechanical properties are desired.

[0004] First, some polyesters and amorphous polymers cannot be used due to their low impact resistance and flexibility. The uses for which it can be used are limited.

[0005] For example, polylactic acid, a typical biomass-derived polyester, is a social Due to the current situation, it has been attracting attention for many years as a substitute for petroleum-derived plastics. Therefore, the applications in which it can be used are limited, and it has not yet come into widespread use. In the field of recycling technology, the mixing of various types of resins is a prerequisite. In other words, problems caused by the incompatibility of the resins tend to occur when a large amount of incompatible resins is mixed. The mechanical properties of recycled resins deteriorate when they are recycled. It was necessary to recycle the resin that had been thoroughly sorted to reduce the amount of impurities. The resin used for packaging is a multi-layer film structure in which different types of resin are firmly laminated. These multilayer films are often used as a structure that cannot be easily separated. Therefore, recycling technology cannot be applied and the materials are discarded.

[0006] In recent years, in order to overcome these problems, the properties of individual resins have been improved by combining multiple resins. Polymer alloy technology is known as a means of compensating for these shortcomings and creating new functions. There are.

[0007] For example, blending polylactic acid with soft polyester improves impact resistance. In this method, the polymer is present as a domain in a polylactic acid matrix. The soft polyester present in the resin acts as a modifier that imparts impact resistance and flexibility. However, the effect of improving impact resistance was not sufficient.

[0008] In addition, a polylactic acid and polyolefin are blended with a compatibilizer to improve impact resistance and heat resistance. However, in order to obtain sufficient impact resistance and heat resistance, Therefore, a large amount of polyolefin was required.

[0009] In addition, by blending core-shell latex with polylactic acid, impact resistance is improved and transparency is improved. There is a method to maintain the transparency (Patent Document 3). In this method, the shell part is incompatible with polylactic acid. The core part provides impact resistance, and the dispersed particle size does not change depending on the kneading method. However, core-shell latex is generally The cost is high in terms of cost, and the material obtained by blending is also high in cost.

[0010] Furthermore, the addition of a compatibilizer has been investigated as a means of recycling laminated composite resins. For example, ionomer resin is used as a compatibilizer to make PE-PET and PP-ABS. The compounding of these has been investigated (Patent Document 4). In addition, an oxazoline-based compatibilizer is used to The composite of PE-PET and the like is being investigated (Patent Document 5). According to these documents, the addition of a compatibilizer It has been shown that the physical properties of PE-PET or EVOH composites can be improved by using However, the recycled resins obtained by these methods do not have sufficient mechanical properties. It is necessary to develop technology that can further improve mechanical properties. Due to problems such as poor recyclability, there were limitations on the uses of recycled resin. .

[0011] Such materials contribute to reducing environmental impact, but materials with further improved brittleness are needed. It is highly desired. [Prior art documents] [Patent documents]

[0012] [Patent Document 1] Japanese Patent Application Laid-Open No. 2004-231772 [Patent Document 2] Japanese Patent Application Laid-Open No. 2008-038142 [Patent Document 3] JP 2015-140361 A [Patent Document 4] Japanese Patent Application Laid-Open No. 2001-220473 [Patent Document 5] Japanese Patent Application Laid-Open No. 2004-182957 [Patent Document 6] Special Publication No. 2009-535452 Summary of the Invention [Problem to be solved by the invention]

[0013] The present invention uses a specific ethylene-acetic acid compound in biomass-derived resins and recycled composite resins. By blending a vinyl acetate copolymer composition, the brittleness is overcome, and the product has excellent impact resistance and flexibility. The present invention aims to provide a resin composition that can be used in a molded article, and a molded article that uses the resin composition. [Means for solving the problem]

[0014] As a result of extensive research to solve the above problems, the present inventors have found that a brittle resin or resin composition A resin composition containing a specific ethylene-vinyl acetate copolymer has been found to have impact resistance and flexibility. The inventors have found that the softness of the film is excellent, and have completed the present invention.

[0015] That is, the present invention provides a thermoplastic resin (A) containing 1% by weight or more and 99% by weight or less of vinyl acetate. Ethylene-vinyl acetate copolymers containing two or more different amounts of ethylene-vinyl acetate copolymers The total of (A) and (B) is 100% by weight or more and 99% by weight or less of the total composition (B). The present invention relates to a resin composition containing the above-mentioned hydroxybenzoates (expressed in % by weight).

[0016] The present invention will be described in detail below.

[0017] The thermoplastic resin (A) of the present invention may be an ethylene-vinyl acetate copolymer composition (B) or a copolymer of the same. Because of its excellent compatibility with polyolefin resins, acrylic resins, and polyamide resins, Grease, polyester resin, polycarbonate resin, polystyrene resin, styrene-acrylic At least one member from the group consisting of nitrile copolymers is preferred.

[0018] Polyolefin resins include high-density polyethylene, low-density polyethylene, linear low-density polyethylene, High density polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-vinyl Alcohol copolymer, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer , ethylene-acrylic acid ester copolymer, ethylene-methacrylic acid ester copolymer, Examples include polybutadiene and polyisoprene.

[0019] Acrylic acid resins include polyacrylic acid, polymethyl acrylate, and polyacrylic acid Ethyl, Polybutyl acrylate, Polyoctyl acrylate, Polymethacrylic acid, Polymeth Methyl acrylate, polyethyl methacrylate, polybutyl methacrylate, polymethacrylic acid Octyl and the like.

[0020] Polyamide resins include nylon 6, nylon 6,6, nylon 11, and nylon 1. Examples include 2.

[0021] Polyester resins include polyethylene terephthalate and glycol-modified polyethylene. Polyethylene terephthalate resin (PETG resin), polybutylene terephthalate, polylactic acid (poly -L-lactic acid, poly-D-lactic acid, copolymer of L-lactic acid and D-lactic acid, poly-L-lactic acid and poly-D- containing stereocomplexes of lactic acid), polybutylene succinate, poly(butylene succinate) succinate / adipate), polyethylene succinate, poly(butylene succinate / terephthalate), poly(butylene adipate / terephthalate), poly(hydroxybutylene Poly(3-hydroxybutylene / hydroxyhexanoate), Polyglycolic acid, Poly(3-hydroxybutylene) Examples of suitable copolymers include acrylate and polycaprolactone.

[0022] Among these, when blended with the ethylene-vinyl acetate copolymer composition (B), the impact resistance is Since the improvement in elongation at break is large, it is suitable for use with polyester resins or acrylic resins. At least one of them is preferred, and biodegradable polyester resins such as polylactic acid and polybutylene are preferred. Succinate, polyglycolic acid, poly(3-hydroxybutyrate), polycaprolactone At least one of the group consisting of polylactic acid and polybutylene is more preferred. The compound is either a benzodiazepine or a benzoxanthate.

[0023] The thermoplastic resin (A) of the present invention may be high density polyethylene, low density polyethylene, straight polyethylene, or the like. 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 (PE TG resin), polybutylene terephthalate, polylactic acid (poly-L-lactic acid, poly-D-lactic acid) , copolymers of L-lactic acid and D-lactic acid, stereocomplexes of poly-L-lactic acid and poly-D-lactic acid At least one member from the group consisting of polybutylene succinate is preferred.

[0024] The thermoplastic resin (A) of the present invention may be polylactic acid (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 At least one member from the group consisting of polybutylene succinate is preferred.

[0025] When the thermoplastic resin (A) is polylactic acid, it is composed mainly of L-lactic acid and / or D-lactic acid. It is a polymer containing lactic acid as a component, but from the viewpoint of heat resistance, polylactic acid resin with high optical purity of lactic acid component is used. It is preferable to use a polylactic acid resin in which the L-form accounts for 80% of the total lactic acid components. It is preferable that the D-isomer contains 80% or more, and the L-isomer contains 90% or more. It is more preferable that the D-isomer is contained in an amount of 90% or more, and the L-isomer is contained in an amount of 95% or more. It is particularly preferable that the D-isomer is contained in an amount of 95% or more, and it is particularly preferable that the L-isomer is contained in an amount of 98% or more. Or, most preferably, the D-isomer accounts for 98% or more.

[0026] The thermoplastic resin (A) of the present invention may be high density polyethylene, low density polyethylene, straight polyethylene, or the like. 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 (PE At least one member selected from the group consisting of TG resin and polybutylene terephthalate is preferred.

[0027] The thermoplastic resin (A) of the present invention may be used alone or as a composite of two or more kinds.

[0028] The thermoplastic resin (A) of the present invention may be an unused virgin resin, a used recovered resin, or a recycled resin. Here, recycled resin is used resin that has been washed, separated from foreign matter, It is a resin that has undergone a process such as sorting. In other words, one or more types of resin are all virgin. A form in which the resin is used, and at least one of the one or more types of resin is used resin The present invention also includes a configuration in which all of the one or more resins are used resins.

[0029] When a recovered or recycled resin is used, the thermoplastic resin (A) of the present invention may be a resin containing a plurality of types of recycled or recycled resins. It may contain resin. In this case, impurities include PVC resin, wax, adhesive, plasticizer, Contains organic impurities such as antioxidants. The total amount of these organic impurities is 3% by weight or less. On the other hand, inorganic impurities may be contained as fillers. When pure substances are included, the content of impurities is It can be expressed as a ratio to the total amount of body composition (B) and impurities.

[0030] The molecular weight and molecular weight distribution of the thermoplastic resin (A) are such that it has sufficient rigidity to be used as a molded article. From this viewpoint, the weight average molecular weight is preferably 10,000 or more, more preferably 50,000 or more, and even more preferably 10,000 or more. The weight average molecular weight here is preferably 100,000 or more. Polystyrene measured by gel permeation chromatography (GPC) using furan. The weight average molecular weight is calculated as polyethylene.

[0031] The melt mass flow rate of the thermoplastic resin (A) is , 0.1g / 10min or more and 50g / 10min or less are preferable, 0.1g / 10min or more and 20g / It is more preferable that the thermoplastic resin (A) is polylactic acid or polybutylene. For succinate, the melt mass flow rate is 0.1g / 10min or more and 20g / 10min or more. Preferably, the range is 1 g / 10 min or more and 10 g / 10 min or less, more preferably 1 g / 10 min or more and 10 g / 10 min or less.

[0032] The ethylene-vinyl acetate copolymer composition (B) of the present invention comprises two or more copolymers having different vinyl acetate contents. It contains the above ethylene-vinyl acetate copolymer.

[0033] Each ethylene-vinyl acetate copolymer in the ethylene-vinyl acetate copolymer composition (B) The vinyl acetate content is preferably 15% by weight or more and 85% by weight or less. The vinyl acid content can be measured by the method of JIS K6924-1.

[0034] The methods for producing ethylene-vinyl acetate copolymer include high-pressure radical polymerization, solution polymerization, and Examples of the resin include known production methods such as emulsion polymerization, and such resins can be conveniently selected from commercially available products. As an ethylene-vinyl acetate copolymer, Ultrathene is available from Tosoh Corporation. These are sold under the trade names Levaprene and Levamelt by Lanxess KK. do.

[0035] The composition of the present invention is the ethylene-vinyl acetate copolymer composition (B), When the difference in vinyl acetate content of the copolymer is taken, the vinyl acetate content of at least one copolymer is The difference is preferably 40% by weight or less. The compatibility between the ethylenediamine-vinyl acetate copolymer is further improved, resulting in improved impact resistance and flexibility of the resulting composition. The difference in vinyl acetate content of at least one pair of copolymers is preferably 35% by weight or less. It is more preferably 30% by weight or less, and most preferably 28% by weight or less.

[0036] In addition, the difference in vinyl acetate content between at least one pair of copolymers is preferably 5% by weight or more. This is preferable. This improves the compatibility between the copolymers, and improves the impact resistance and flexibility of the resulting composition.

[0037] Here, in the ethylene-vinyl acetate copolymer composition (B), the acetate of each copolymer The difference in vinyl content is, for example, three vinyl acetate contents of 25 wt%, 50 wt%, and 80 wt%. Ethylene-vinyl acetate copolymers (hereinafter referred to as VAc25, ... For a composition containing hydroxybenzoates (hereinafter referred to as Ac50 and VAc80), the following calculation can be made:

[0038] VAc50 - VAc25 = 25% by weight VAc80 - VAc50 = 30% by weight VAc80 - VAc25 = 55% by weight

[0039] The composition of the present invention is the ethylene-vinyl acetate copolymer composition (B), When taking the difference in vinyl acetate content of the polymer, the difference in each vinyl acetate content is It is preferable that the content is 70% by weight or less. This further improves the transparency of the resulting composition. The difference in all vinyl acetate contents is preferably 60% by weight or less.

[0040] It is also preferable that the difference in vinyl acetate content between the two is 5% by weight or more. Compatibility between thermoplastic resin (A) and ethylene-vinyl acetate copolymer constituting composition (B) This further improves the impact resistance and flexibility of the resulting composition.

[0041] The ethylene-vinyl acetate copolymer composition (B) of the present invention comprises three or more types of copolymers having different vinyl acetate contents. It is preferable that the above ethylene-vinyl acetate copolymer is contained. In this case, the following It is preferred that the resin contains an ethylene-vinyl acetate copolymer.

[0042] Ethylene-vinyl acetate copolymer with a vinyl acetate content of 15% by weight or more and 30% by weight or less Ethylene-vinyl acetate copolymer with a vinyl acetate content of 45% by weight or more and 55% by weight or less Ethylene-vinyl acetate copolymer with a vinyl acetate content of 75% by weight or more and 85% by weight or less In order to satisfy these requirements, the ethylene-vinyl acetate copolymer composition (B) The ethylene-vinyl acetate copolymer can be adjusted by using two or more kinds, preferably three or more kinds. Ethylene vinyl acetate copolymer with a vinyl acetate content of 25% by weight is designated as VAc25. If the composition of the components is expressed as (+), for example, (VAc25+VAc40), (VAc25 +VAc50), (VAc50+VAc80), (VAc25+VAc50+VAc80 ), (VAc25+VAc50+VAc70+VAc80), (VAc25+VAc40 +VAc50+VAc70), VAc25+VAc40+VAc50+VAc70+VA c80) are examples.

[0043] The ethylene-vinyl acetate copolymer constituting the ethylene-vinyl acetate copolymer composition (B) of the present invention The vinyl copolymer may be crosslinked.

[0044] As a crosslinking modification method, a crosslinking agent is added to the ethylene-vinyl acetate copolymer composition (B). The crosslinking agent is not particularly limited as long as it can crosslink each component. Although it is not necessary to use organic peroxides, it is preferable to use organic peroxides in consideration of reactivity and the like.

[0045] The organic peroxide used as the crosslinking agent is not particularly limited as long as it is an organic peroxide. For example, Di-t-butyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-di(t-butyl) 1,1-di(t-butylperoxy)hexane, 2, 5-Dimethyl-2,5-di(t-butylperoxy)hexyne-3,1,3-bis(t- butylperoxyisopropyl)benzene, 1,1-bis(t-butylperoxy)-3 ,3,5-trimethylcyclohexane, 1,3-di-(t-butylperoxy)-diisopropyl Propylbenzene, n-butyl-4,4-bis(t-butylperoxy)valerate, p-Chlorobenzoyl peroxide, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, t-butyl peroxybenzoate, t-butyl peroxyisopropyl Carbonate, Diacetyl Peroxide, Lauroyl Peroxide, t-Butyl Cumyl These may be used alone or in combination of two or more. It can be used.

[0046] Among them, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, 1,1 Di(t-butylperoxy)cyclohexane is preferably used from the viewpoint of reactivity. In addition to the crosslinking agent, triallyl isocyanurate, divinylbenzene, etc. may be used as needed. A crosslinking aid such as methacrylate may also be used.

[0047] The ethylene-vinyl acetate copolymer composition (B) containing the crosslinking agent is heated and kneaded. In this case, the kneading temperature is set to 100°C. The melting point of the component (B) to about 300°C is preferred.

[0048] The ethylene-vinyl acetate copolymer composition (B) of the present invention is a thermoplastic resin ( A) to improve compatibility with vinyl acetate, which is converted to vinyl alcohol by hydrolysis. That's fine.

[0049] The hydrolysis method is not particularly limited, but the ethylene-vinyl acetate copolymer composition (B It is preferable to directly hydrolyze the pellets of ethylene acetate in an alkali. The saponification degree of the vinyl acid copolymer composition (B) is preferably 10% by weight or more. If so, the compatibility with the thermoplastic resin (A) is improved.

[0050] Here, the degree of saponification can be measured in accordance with JIS K7192 (1999). do.

[0051] Thermoplastic resin (A) and ethylene-vinyl acetate copolymer composition in the resin composition of the present invention The mixing ratio of the thermoplastic resin (A) and the material (B) is 1% by weight or more and 99% by weight or less of ethylene The vinyl acetate copolymer composition (B) is preferably contained in an amount of 1% by weight to 99% by weight. The resin composition obtained by containing 99% by weight or less of the thermoplastic resin (A) has excellent impact resistance. On the other hand, when the thermoplastic resin is contained in an amount of 1% by weight or more, the resin composition obtained becomes rigid. The composition of the present invention is more preferably a composition containing 30% by weight of the thermoplastic resin (A). % or more and 95% or less by weight, and 5% or more and 70% or less by weight of ethylene-vinyl acetate copolymer composition (B). % by weight, and more preferably 50% by weight or more and 90% by weight or less of the thermoplastic resin (A). The ethylene-vinyl acetate copolymer composition (B) is contained in an amount of 10% by weight to 50% by weight.

[0052] The resin composition of the present invention comprises a thermoplastic resin (A) and an ethylene-vinyl acetate copolymer composition ( The composition can be produced by a production method including a kneading step of kneading B).

[0053] As a method for kneading the resin composition of the present invention, the thermoplastic resin (A) and ethylene vinyl acetate are mixed. a method in which the various materials constituting the vinyl copolymer composition (B) are simultaneously kneaded in a kneading device; The ethylene-vinyl acetate copolymer composition (B) alone is pre-mixed, and then the thermoplastic resin (A) is added. and kneading the resulting ethylene-vinyl acetate copolymer composition (B) with the resulting ethylene-vinyl acetate copolymer composition (B). The latter allows the ethylene-vinyl acetate copolymer composition (B) to be mixed more uniformly. This is preferred because the desired physical properties can be stably obtained.

[0054] There are no particular limitations on the kneading device as long as it can uniformly disperse each component. For example, a single-screw extruder, a twin-screw extruder, or a multi-screw extruder can be used. , Banbury mixer, pressure kneader, rotating roll, internal mixer, etc. Among these, twin-screw extruders are preferred due to their excellent dispersibility and continuous productivity. More preferable.

[0055] When kneading with a twin-screw extruder, the screw rotation speed is not particularly limited, but it is preferably 50 rpm or more. It is preferable to knead at 3000 rpm or less, and more preferably at 300 rpm or more. The rotation speed is preferably 500 rpm or more and more preferably 3000 rpm or less. If the rotation speed is 50 rpm or more, the dispersion of each mixed component will be improved and the quality of the resulting resin will be improved. If the screw rotation speed is 3000 rpm or less, excessive shear heat generation will occur. This is preferred because the resin does not deteriorate due to oxidation, and the resulting resin has excellent physical properties.

[0056] When an extruder is used in the kneading step, the resin composition kneaded in the extruder is preferably The resin composition is kneaded under high-speed shear conditions of 50 rpm to 3000 rpm as a raw material. In addition, the molded product obtained by extrusion molding in an extruder can be used as it is. It can be used as a molded product.

[0057] The kneading temperature is the melting point of the thermoplastic resin (A) or the glass transition temperature of the amorphous resin (B) to 30°C. A temperature of around 0°C is preferable.

[0058] The resin composition of the present invention may further contain an antistatic agent, a light stabilizer, or the like, within the range not impairing the effects of the present invention. agents, UV absorbers, nucleating agents, lubricants, antioxidants, anti-blocking agents, flow improvers, Mold agent, flame retardant, colorant, inorganic neutralizer, hydrochloric acid absorbent, filler conductive agent, chain extender, hydrolyzer An anti-unwinding agent or the like may also be used.

[0059] When the resin composition of the present invention contains components other than (A) and (B), the content of the components other than (A) and (B) is The total of A) and (B) is 100 parts by weight, and the amount added is expressed as the amount per 100 parts by weight. In other words, the expression "% by weight" of (A) and (B) means that (A) and (B) ) and the ratio of other components can be defined separately.

[0060] The resin composition of the present invention may be used in any form such as pellets or powder. It is possible.

[0061] The resin composition of the present invention may be molded by any method, for example, by profile extrusion, film, sheet, or block. These include wax, injection molding, foaming, extrusion coating, and rotational molding.

[0062] Molded articles made from the resin composition of the present invention are useful for automobile parts, housings for electric and electronic parts, building materials, soil It can be used for a variety of purposes, including wood materials, agricultural materials, containers, packaging materials, adhesives, and daily necessities. do.

[0063] In another embodiment of the present invention, two or more ethylene-vinyl acetate copolymers having different vinyl acetate contents are used. The impact modifier comprises a copolymer composition, which is the ethylene vinyl acetate copolymer described above. This means that the copolymer composition (B) is included.

[0064] In addition, the modifier according to another embodiment of the present invention is capable of compatibilizing at least two types of resins. The resin to be recycled can be suitably used for recycling. is the thermoplastic resin (A) described above. In practice, high density polyethylene, low density polyethylene, Polyethylene, linear low-density polyethylene, polypropylene, ethylene-propylene copolymer, ethylene Polyethylene-vinyl alcohol copolymer, nylon 6, nylon 6,6, nylon 11, nylon Polyethylene terephthalate, glycol-modified polyethylene terephthalate resin (PETG resin), polybutylene terephthalate, It can be used. [Effects of the Invention]

[0065] The resin composition of the present invention is excellent in impact resistance and elongation at break, and is suitable for use in components that require these physical properties. It is useful for shaping products. [Example]

[0066] The present invention will be described below with reference to examples and comparative examples, but the present invention is not limited to these. It's not that.

[0067] (1) Melt mass flow rate (MFR) The MFR of the ethylene-vinyl acetate copolymer and the thermoplastic resin (A) is Measurements were taken at 190°C and a load of 2.16 kg using a CUSA (manufactured by Takara Kogyo). (2) Vinyl acetate content The vinyl acetate content was measured in accordance with JIS K6924-1. (3) Impact strength Impact strength was measured in accordance with JIS P 8134. Press-molded thickness 0.1 mm The sheet was subjected to a test with a film impact tester (FT-M type, manufactured by Toyo Seiki) with a test capacity of 3J. Measurement was carried out under the condition of a hemispherical hammer with a piercing tip. (4) Tensile test A tensile test was conducted as a flexibility test. A press-molded sheet with a thickness of 0.1 mm was placed on the AS TM D-1822-L A dumbbell-shaped test piece was punched out. The test piece size was 63 mm in total length. 0.5mm, parallel part length 9.53mm, parallel part width 3.18mm, thickness 0.1mm, grip part The test piece was 9.53 mm wide. The test piece was placed on a Tensilon tensile tester (manufactured by Orientec, RTE- 1210) under the conditions of a chuck distance of 30 mm and a pulling speed of 200 mm / min. The point at which the sample broke was determined as the breaking elongation (breaking elongation [%] = tensile length required to break [mm] / chuck The distance between the blocks was 30 mm.

[0068] Example 1 Thermoplastic resin (A) has an L-isomer ratio of 98.5%, a D-isomer ratio of 1.5%, and a weight-average molecular weight of 1 Polylactic acid ( A-1) (NatureWorks, Inc., product name Ingeo4032D) 90 layers % by weight, and the ethylene-vinyl acetate copolymer composition (B) is an ethylene-vinyl acetate copolymer having the following composition: 10% by weight of the copolymer was used.

[0069] Ethylene vinyl acetate content 25% by weight, melt mass flow rate 3g / 10min Vinyl acetate copolymer (B-25) (manufactured by Tosoh Corporation, trade name Ultrathene 640) 5 wt. % Ethylene with a vinyl acetate content of 50% by weight and a melt mass flow rate of 3 g / 10 min Vinyl acetate copolymer (B-50) (manufactured by LANXESS KK, trade name Levaprene 500) 5-ply amount% A thermoplastic resin (A) and an ethylene-vinyl acetate copolymer composition (B) are dry-blended. The resin temperature was then measured using an internal mixer (Toyo Seiki, product name: Labo Blast Mill R-100). The mixture was melt-kneaded under the conditions of a temperature of 180°C, a roller rotation speed of 60 rpm, and a kneading time of 5 minutes.

[0070] The obtained kneaded material was pressed into a press molding machine (AWFA-50 manufactured by Shinto Metal Industries Co., Ltd.) Pressure 10MPa, heating temperature 200℃ (primary pressure x 3 minutes, secondary pressure x 3 minutes), cooling temperature 25 The mixture was press-molded at 200°C for 4 minutes to obtain a pressed sheet having a thickness of 0.1 mm.

[0071] The obtained press sheet was subjected to a tensile test and an impact test. The evaluation results are shown in Table 1. show.

[0072] Example 2 The same procedure was carried out except that the composition of 10% by weight of the ethylene-vinyl acetate copolymer composition (B) was as follows: A press sheet was obtained in the same manner as in Example 1.

[0073] Ethylene vinyl acetate content 25% by weight, melt mass flow rate 3g / 10min Vinyl acetate copolymer (B-25) (manufactured by Tosoh Corporation, trade name Ultrathene 640) 4 weight % Ethylene with a vinyl acetate content of 50% by weight and a melt mass flow rate of 3 g / 10 min Vinyl acetate copolymer (B-50) (manufactured by LANXESS KK, trade name Levaprene 500) triple layer amount% Ethylene vinyl acetate content 80% by weight, melt mass flow rate 5g / 10min Vinyl acetate copolymer (B-80) (manufactured by LANXESS KK, trade name Levaprene 800) triple layer amount% The obtained press sheet was subjected to a tensile test and an impact test. The evaluation results are shown in Table 1. show.

[0074] Example 3 Thermoplastic resin (A) has an L-isomer ratio of 98.5%, a D-isomer ratio of 1.5%, and a weight-average molecular weight of 1 Polylactic acid ( A-1) (NatureWorks, Inc., product name Ingeo 4032D) 80 weight %, and as the ethylene-vinyl acetate copolymer composition (B), an ethylene-vinyl acetate copolymer having the following composition: A press sheet was obtained in the same manner as in Example 1, except that 20% by weight of the copolymer was used.

[0075] Ethylene vinyl acetate content 25% by weight, melt mass flow rate 3g / 10min Vinyl acetate copolymer (B-25) (Tosoh Corporation, product name Ultrathene 640) 10 layers amount% Ethylene with a vinyl acetate content of 50% by weight and a melt mass flow rate of 3 g / 10 min Vinyl acetate copolymer (B-50) (manufactured by LANXESS KK, trade name: Levaprene 500) 10 weight% The obtained press sheet was subjected to a tensile test and an impact test. The evaluation results are shown in Table 1. show.

[0076] Example 4 The same procedure was carried out except that the composition of 20% by weight of the ethylene-vinyl acetate copolymer composition (B) was as follows: A press sheet was obtained in the same manner as in Example 3.

[0077] Ethylene vinyl acetate content 25% by weight, melt mass flow rate 3g / 10min Vinyl acetate copolymer (B-25) (manufactured by Tosoh Corporation, trade name Ultrathene 640) 6 wt. % Ethylene with a vinyl acetate content of 50% by weight and a melt mass flow rate of 3 g / 10 min Vinyl acetate copolymer (B-50) (manufactured by LANXESS KK, trade name Levaprene 500) 9-ply amount% Ethylene vinyl acetate content 80% by weight, melt mass flow rate 5g / 10min Vinyl acetate copolymer (B-80) (manufactured by LANXESS KK, trade name Levaprene 800) 5-ply amount% The obtained press sheet was subjected to a tensile test and an impact test. The evaluation results are shown in Table 1. show.

[0078] Example 5 The same procedure was carried out except that the composition of 20% by weight of the ethylene-vinyl acetate copolymer composition (B) was as follows: A press sheet was obtained in the same manner as in Example 3.

[0079] Ethylene vinyl acetate content 25% by weight, melt mass flow rate 3g / 10min Vinyl acetate copolymer (B-25) (manufactured by Tosoh Corporation, trade name Ultrathene 640) 6 wt. % Ethylene with a vinyl acetate content of 40% by weight and a melt mass flow rate of 3 g / 10 min Vinyl acetate copolymer (B-40) (manufactured by LANXESS KK, trade name Levaprene 400) triple layer amount% Ethylene with a vinyl acetate content of 50% by weight and a melt mass flow rate of 3 g / 10 min Vinyl acetate copolymer (B-50) (manufactured by LANXESS KK, trade name Levaprene 500) 4-ply amount% Ethylene vinyl acetate content 70% by weight, melt mass flow rate 5g / 10min Vinyl acetate copolymer (B-70) (manufactured by LANXESS KK, trade name Levaprene 700) double layer amount% Ethylene vinyl acetate content 80% by weight, melt mass flow rate 5g / 10min Vinyl acetate copolymer (B-80) (manufactured by LANXESS KK, trade name Levaprene 800) 5-ply amount% The obtained press sheet was subjected to a tensile test and an impact test. The evaluation results are shown in Table 1. show.

[0080] Example 6 Thermoplastic resin (A) has an L-isomer ratio of 98.5%, a D-isomer ratio of 1.5%, and a weight-average molecular weight of 1 Polylactic acid ( A-1) (NatureWorks, Inc., product name Ingeo 4032D) 70 weight %, and as the ethylene-vinyl acetate copolymer composition (B), an ethylene-vinyl acetate copolymer having the following composition: A press sheet was obtained in the same manner as in Example 1, except that 30% by weight of the copolymer was used.

[0081] Ethylene vinyl acetate content 25% by weight, melt mass flow rate 3g / 10min Vinyl acetate copolymer (B-25) (manufactured by Tosoh Corporation, trade name Ultrathene 640) 9 weight % Ethylene with a vinyl acetate content of 40% by weight and a melt mass flow rate of 3 g / 10 min Vinyl acetate copolymer (B-40) (manufactured by LANXESS KK, trade name Levaprene 400) 4-ply amount% Ethylene with a vinyl acetate content of 50% by weight and a melt mass flow rate of 3 g / 10 min Vinyl acetate copolymer (B-50) (manufactured by LANXESS KK, trade name Levaprene 500) 6-ply amount% Ethylene vinyl acetate content 70% by weight, melt mass flow rate 5g / 10min Vinyl acetate copolymer (B-70) (manufactured by LANXESS KK, trade name Levaprene 700) triple layer amount% Ethylene vinyl acetate content 80% by weight, melt mass flow rate 5g / 10min Vinyl acetate copolymer (B-80) (manufactured by LANXESS KK, trade name Levaprene 800) 8 layers amount% The obtained press sheet was subjected to a tensile test and an impact test. The evaluation results are shown in Table 1. show.

[0082] Example 7 Thermoplastic resin (A) has an L-isomer ratio of 98.5%, a D-isomer ratio of 1.5%, and a weight-average molecular weight of 1 Polylactic acid ( A-1) (NatureWorks, Inc., product name Ingeo 4032D) 50 weight %, and as the ethylene-vinyl acetate copolymer composition (B), an ethylene-vinyl acetate copolymer having the following composition: A press sheet was obtained in the same manner as in Example 1, except that 50% by weight of the copolymer was used.

[0083] Ethylene vinyl acetate content 25% by weight, melt mass flow rate 3g / 10min Vinyl acetate copolymer (B-25) (Tosoh Corporation, product name Ultrathene 640) 15 layers amount% Ethylene with a vinyl acetate content of 40% by weight and a melt mass flow rate of 3 g / 10 min Vinyl acetate copolymer (B-40) (manufactured by LANXESS KK, trade name Levaprene 400) 7-ply amount% Ethylene with a vinyl acetate content of 50% by weight and a melt mass flow rate of 3 g / 10 min Vinyl acetate copolymer (B-50) (manufactured by LANXESS KK, trade name: Levaprene 500) 10 weight% Ethylene vinyl acetate content 70% by weight, melt mass flow rate 5g / 10min Vinyl acetate copolymer (B-70) (manufactured by LANXESS KK, trade name Levaprene 700) 5-ply amount% Ethylene vinyl acetate content 80% by weight, melt mass flow rate 5g / 10min Vinyl acetate copolymer (B-80) (Levaprene 800, manufactured by Lanxess KK) 13 weight% The obtained press sheet was subjected to a tensile test and an impact test. The evaluation results are shown in Table 2. show.

[0084] Example 8 The ethylene-vinyl acetate copolymer composition (B) is a crosslinked ethylene-vinyl acetate copolymer. The same procedure as in Example 3 was repeated except that 20% by weight of the polymer composition (B-crosslinked) was used. However, the crosslinked ethylene-vinyl acetate copolymer composition (B-crosslinked) was obtained as follows. was obtained by the method.

[0085] The ethylene-vinyl acetate copolymer composition having the following composition and an organic peroxide (Japanese) as a crosslinking agent Oil Co., Ltd. (trade name: Perhexa 25B) was used for the ethylene-vinyl acetate copolymer composition. The mixture was blended at 0.02% by weight and mixed in an internal mixer (manufactured by Toyo Seiki, product name: Labo Blast Mixer). R-100) under the conditions of resin temperature 180°C, roller rotation speed 60 rpm, and kneading time 2 minutes. The mixture was melt-kneaded at 100°C to obtain an ethylene-vinyl acetate copolymer composition (B-crosslinked).

[0086] Ethylene vinyl acetate content 25% by weight, melt mass flow rate 3g / 10min Vinyl acetate copolymer (B-25) (manufactured by Tosoh Corporation, trade name Ultrathene 640) 6 wt. % Ethylene with a vinyl acetate content of 40% by weight and a melt mass flow rate of 3 g / 10 min Vinyl acetate copolymer (B-40) (manufactured by LANXESS KK, trade name Levaprene 400) triple layer amount% Ethylene with a vinyl acetate content of 50% by weight and a melt mass flow rate of 3 g / 10 min Vinyl acetate copolymer (B-50) (manufactured by LANXESS KK, trade name Levaprene 500) 4-ply amount% Ethylene vinyl acetate content 70% by weight, melt mass flow rate 5g / 10min Vinyl acetate copolymer (B-70) (manufactured by LANXESS KK, trade name Levaprene 700) double layer amount% Ethylene vinyl acetate content 80% by weight, melt mass flow rate 5g / 10min Vinyl acetate copolymer (B-80) (manufactured by LANXESS KK, trade name Levaprene 800) 5-ply amount% The obtained press sheet was subjected to a tensile test and an impact test. The evaluation results are shown in Table 2. show.

[0087] Example 9 The ethylene-vinyl acetate copolymer composition (B) is a saponified ethylene-vinyl acetate copolymer. The same procedure as in Example 1 was repeated except that 20% by weight of the saponified vinyl copolymer composition (B) was used. A press sheet was obtained. However, the saponified ethylene-vinyl acetate copolymer composition (B- Saponified) was obtained by the following method.

[0088] The crosslinked ethylene-vinyl acetate copolymer composition (B-crosslinked) described in Example 8 was used in a single layer. The mixture was hydrolyzed in a methanol solution of sodium hydroxide at 60°C and saponified. A saponified ethylene-vinyl acetate copolymer composition (B-saponified) was obtained.

[0089] The obtained press sheet was subjected to a tensile test and an impact test. The evaluation results are shown in Table 2. show.

[0090] Example 10 The same procedure was carried out except that the composition of 20% by weight of the ethylene-vinyl acetate copolymer composition (B) was as follows: A press sheet was obtained in the same manner as in Example 3.

[0091] Ethylene vinyl acetate content 25% by weight, melt mass flow rate 3g / 10min Vinyl acetate copolymer (B-25) (Tosoh Corporation, product name Ultrathene 640) 10 layers amount% Ethylene vinyl acetate content 80% by weight, melt mass flow rate 5g / 10min Vinyl acetate copolymer (B-80) (manufactured by LANXESS KK, trade name: Levaprene 800) 10 weight% The obtained press sheet was subjected to a tensile test and an impact test. The evaluation results are shown in Table 2. show.

[0092] Comparative Example 1 Thermoplastic resin (A) L-body ratio 98.5%, D-body ratio 1.5%, melt mass flow Polylactic acid (A-1) (NatureWorks) with a melting point of 170°C and a melting rate of 4g / 10min. The same procedure as in Example 1 was used except that 100% by weight of Ingeo 4032D (manufactured by Ingeo Chemical Industries, Ltd.) was used. A press sheet was obtained by the above method.

[0093] The obtained press sheet was subjected to a tensile test and an impact test. The evaluation results are shown in Table 2. show.

[0094] Comparative Example 2 Ethylene-vinyl acetate copolymer composition (B) containing 25% by weight of vinyl acetate and melt Ethylene-vinyl acetate copolymer (B-25) (Tosoko) with a mass flow rate of 3 g / 10 min. The same procedure as in Example 3 was repeated except that only 20% by weight of Ultrathene 640 (manufactured by FUJIFILM Holdings Co., Ltd.) was used. A press sheet was obtained by the above method.

[0095] The obtained press sheet was subjected to a tensile test and an impact test. The evaluation results are shown in Table 2. show.

[0096] [Table 1]

[0097] [Table 2]

[0098] Example 11 Thermoplastic resin (A) has a melt mass flow rate of 5 g / 10 min and a melting point of 115°C. Polybutylene succinate (A-2) (manufactured by Mitsubishi Chemical Corporation, trade name GSPla FZ9 1) 80% by weight, and ethylene-vinyl acetate copolymer composition (B) 20% by weight, A press sheet was obtained in the same manner as in Example 1, except for the above.

[0099] Ethylene vinyl acetate content 25% by weight, melt mass flow rate 3g / 10min Vinyl acetate copolymer (B-25) (manufactured by Tosoh Corporation, trade name Ultrathene 640) 5 wt. % Ethylene with a vinyl acetate content of 50% by weight and a melt mass flow rate of 3 g / 10 min Vinyl acetate copolymer (B-50) (manufactured by LANXESS KK, trade name Levaprene 500) 5-ply amount% Ethylene vinyl acetate content 80% by weight, melt mass flow rate 5g / 10min Vinyl acetate copolymer (B-80) (manufactured by LANXESS KK, trade name: Levaprene 800) 10 weight% The obtained press sheet was subjected to a tensile test and an impact test. The evaluation results are shown in Table 3. show.

[0100] Example 12 The same procedure was carried out except that the composition of 20% by weight of the ethylene-vinyl acetate copolymer composition (B) was as follows: A pressed sheet was obtained in the same manner as in Example 11.

[0101] Ethylene vinyl acetate content 25% by weight, melt mass flow rate 3g / 10min Vinyl acetate copolymer (B-25) (manufactured by Tosoh Corporation, trade name Ultrathene 640) 2 wt. % Ethylene with a vinyl acetate content of 40% by weight and a melt mass flow rate of 3 g / 10 min Vinyl acetate copolymer (B-40) (manufactured by LANXESS KK, trade name Levaprene 400) double layer amount% Ethylene with a vinyl acetate content of 50% by weight and a melt mass flow rate of 3 g / 10 min Vinyl acetate copolymer (B-50) (manufactured by LANXESS KK, trade name Levaprene 500) triple layer amount% Ethylene vinyl acetate content 70% by weight, melt mass flow rate 5g / 10min Vinyl acetate copolymer (B-70) (manufactured by LANXESS KK, trade name Levaprene 700) triple layer amount% Ethylene vinyl acetate content 80% by weight, melt mass flow rate 5g / 10min Vinyl acetate copolymer (B-80) (manufactured by LANXESS KK, trade name: Levaprene 800) 10 weight% The obtained press sheet was subjected to a tensile test and an impact test. The evaluation results are shown in Table 3. show.

[0102] Example 13 The crosslinked ethylene-vinyl acetate copolymer composition (B) described in Example 8 was used as 20% by weight. The same procedure as in Example 11 was repeated except that the ethylene-vinyl acetate copolymer composition (B-crosslinked) was used. A press sheet was obtained by this method.

[0103] The obtained press sheet was subjected to a tensile test and an impact test. The evaluation results are shown in Table 3. show.

[0104] Example 14 20% by weight of the ethylene-vinyl acetate copolymer composition (B) was prepared by saponifying the ethylene-vinyl acetate copolymer composition (B) described in Example 9. Example 11 except that the treated ethylene-vinyl acetate copolymer composition (B-saponified) was used A press sheet was obtained by the same method as in the above.

[0105] The obtained press sheet was subjected to a tensile test and an impact test. The evaluation results are shown in Table 3. show.

[0106] Comparative Example 3 Thermoplastic resin (A) has a melt mass flow rate of 5 g / 10 min and a melting point of 115°C. Polybutylene succinate (A-2) (manufactured by Mitsubishi Chemical Corporation, trade name GSPla FZ9 1) A pressed sheet was obtained in the same manner as in Example 11, except that 100% by weight was used. The obtained press sheet was subjected to a tensile test and an impact test. The evaluation results are shown in Table 3. show.

[0107] Comparative Example 4 Ethylene-vinyl acetate copolymer composition (B) containing 25% by weight of vinyl acetate and melt Ethylene-vinyl acetate copolymer (B-25) (Tosoko) with a mass flow rate of 3 g / 10 min. The same procedure as in Example 11 was carried out except that only 20% by weight of Ultrathene 640 (manufactured by FUJIFILM Holdings Co., Ltd.) was used. The pressed sheets were obtained by the same method. The obtained pressed sheets were used for tensile tests and impact tests. The results of the evaluation are shown in Table 3.

[0108] [Table 3]

[0109] Example 15 Thermoplastic resin (A) melt mass flow rate 0.2 g / 10 min, glass transition temperature Polymethyl methacrylate (A-3) (manufactured by Kuraray Co., Ltd., trade name Parapet) 80% by weight of (G-1000) and 20% by weight of ethylene-vinyl acetate copolymer composition (B). A press sheet was obtained in the same manner as in Example 1, except that the composition was as follows.

[0110] Ethylene vinyl acetate content 25% by weight, melt mass flow rate 3g / 10min Vinyl acetate copolymer (B-25) (manufactured by Tosoh Corporation, trade name Ultrathene 640) 6 wt. % Ethylene with a vinyl acetate content of 40% by weight and a melt mass flow rate of 3 g / 10 min Vinyl acetate copolymer (B-40) (manufactured by LANXESS KK, trade name Levaprene 400) triple layer amount% Ethylene with a vinyl acetate content of 50% by weight and a melt mass flow rate of 3 g / 10 min Vinyl acetate copolymer (B-50) (manufactured by LANXESS KK, trade name Levaprene 500) 4-ply amount% Ethylene vinyl acetate content 70% by weight, melt mass flow rate 5g / 10min Vinyl acetate copolymer (B-70) (manufactured by LANXESS KK, trade name Levaprene 700) double layer amount% Ethylene vinyl acetate content 80% by weight, melt mass flow rate 5g / 10min Vinyl acetate copolymer (B-80) (manufactured by LANXESS KK, trade name Levaprene 800) 5-ply amount% The obtained press sheet was subjected to a tensile test and an impact test. The evaluation results are shown in Table 4. show.

[0111] Example 16 The crosslinked ethylene-vinyl acetate copolymer composition (B) described in Example 8 was used as 20% by weight. The same procedure as in Example 15 was repeated except that the ethylene-vinyl acetate copolymer composition (B-crosslinked) was used. A press sheet was obtained by this method.

[0112] The obtained press sheet was subjected to a tensile test and an impact test. The evaluation results are shown in Table 4. show.

[0113] Comparative Example 5 Thermoplastic resin (A) melt mass flow rate 0.2 g / 10 min, glass transition temperature Polymethyl methacrylate (A-3) (manufactured by Kuraray Co., Ltd., trade name Parapet) A press sheet was prepared in the same manner as in Example 15, except that 100% by weight of PEG-1000 was used. I got the point.

[0114] The obtained press sheet was subjected to a tensile test and an impact test. The evaluation results are shown in Table 4. The impact strength and elongation at break were poor.

[0115] Comparative Example 6 Ethylene-vinyl acetate copolymer composition (B) containing 25% by weight of vinyl acetate and melt Ethylene-vinyl acetate copolymer (B-25) (Tosoko) with a mass flow rate of 3 g / 10 min. The same procedure as in Example 15 was carried out except that only 20% by weight of Ultrathene 640 (manufactured by FUJIFILM Holdings Co., Ltd.) was used. The pressed sheets were obtained by the same method. The obtained pressed sheets were used for tensile tests and impact tests. The evaluation results are shown in Table 4. The impact strength and elongation at break were poor.

[0116] [Table 4]

[0117] Example 17 The thermoplastic resin (A) is 70% by weight of a thermoplastic resin composition having the following composition, and ethylene - As the vinyl acetate copolymer composition (B), ethylene-vinyl acetate copolymer 30% of the following composition was used. Weight percent was used. [Thermoplastic resin (A) composition] High-density polyethylene with a melt mass flow rate of 5.5g / 10min and a melting point of 133℃ (A-4) (Nipolon HD4020, manufactured by Tosoh Corporation) 17.5% by weight Polypropylene (A) with a melt mass flow rate of 6.5 g / 10 min and a melting point of 137°C -5) (Novatec PP FW4BT, manufactured by Japan Polypropylene Corporation) 17.5% by weight PETG resin (A-6) (manufactured by Eastman Chemical Company) with a glass transition temperature of 67°C Product name Eastar GN5011) 17.5% by weight Ethylene-vinyl alcohol copolymer with ethylene content of 35 mol% and melting point of 177℃ Substance (A-7) (manufactured by Kuraray Co., Ltd., trade name EVAL C109B) 17.5% by weight [Ethylene-vinyl acetate copolymer composition (B)] Ethylene vinyl acetate content 25% by weight, melt mass flow rate 3g / 10min Vinyl acetate copolymer (B-25) (Tosoh Corporation, product name Ultrathene 640) 15 layers amount% Ethylene with a vinyl acetate content of 50% by weight and a melt mass flow rate of 3 g / 10 min Vinyl acetate copolymer (B-50) (Levaprene 500, manufactured by Lanxess KK) 7. 5% by weight Ethylene vinyl acetate content 80% by weight, melt mass flow rate 5g / 10min Vinyl acetate copolymer (B-80) (Levaprene 800, manufactured by Lanxess KK) 7. 5% by weight Thermoplastic resins (A-4) to (A-7) and an ethylene-vinyl acetate copolymer composition (B) Dry blend and then mix in an internal mixer (Toyo Seiki, product name: Labo Blast Mill R-1 00) at a resin temperature of 200°C, a roller rotation speed of 60 rpm, and a kneading time of 5 minutes. Mixing was carried out.

[0118] The obtained kneaded material was pressed into a press molding machine (AWFA-50 manufactured by Shinto Metal Industries Co., Ltd.) Pressure 10MPa, heating temperature 200℃ (primary pressure x 3 minutes, secondary pressure x 3 minutes), cooling temperature 25 The mixture was press-molded at 200°C for 4 minutes to obtain a pressed sheet having a thickness of 0.1 mm.

[0119] The obtained press sheet was subjected to a tensile test and an impact test. The evaluation results are shown in Table 5. show.

[0120] Example 18 The same procedure was carried out except that the composition of 30% by weight of the ethylene-vinyl acetate copolymer composition (B) was as follows: A pressed sheet was obtained in the same manner as in Example 17.

[0121] Ethylene vinyl acetate content 25% by weight, melt mass flow rate 3g / 10min Vinyl acetate copolymer (B-25) (manufactured by Tosoh Corporation, trade name Ultrathene 640) 9 weight % Ethylene with a vinyl acetate content of 40% by weight and a melt mass flow rate of 3 g / 10 min Vinyl acetate copolymer (B-40) (manufactured by LANXESS KK, trade name Levaprene 400) 4-ply amount% Ethylene with a vinyl acetate content of 50% by weight and a melt mass flow rate of 3 g / 10 min Vinyl acetate copolymer (B-50) (manufactured by LANXESS KK, trade name Levaprene 500) 6-ply amount% Ethylene vinyl acetate content 70% by weight, melt mass flow rate 5g / 10min Vinyl acetate copolymer (B-70) (manufactured by LANXESS KK, trade name Levaprene 700) triple layer amount% Ethylene vinyl acetate content 80% by weight, melt mass flow rate 5g / 10min Vinyl acetate copolymer (B-80) (manufactured by LANXESS KK, trade name Levaprene 800) 8 layers amount% The obtained press sheet was subjected to a tensile test and an impact test. The evaluation results are shown in Table 5. show.

[0122] Comparative Example 7 The thermoplastic resin (A) was 100% by weight of a thermoplastic resin composition having the following composition: A press sheet was obtained in the same manner as in Example 17.

[0123] High-density polyethylene with a melt mass flow rate of 5.5g / 10min and a melting point of 133℃ (A-4) (Nipolon HD4020, manufactured by Tosoh Corporation) 17.5% by weight Polypropylene (A) with a melt mass flow rate of 6.5 g / 10 min and a melting point of 137°C -5) (Novatec PP FW4BT, manufactured by Japan Polypropylene Corporation) 17.5% by weight PETG resin (A-6) (manufactured by Eastman Chemical Company) with a glass transition temperature of 67°C Product name Eastar GN5011) 17.5% by weight Ethylene-vinyl alcohol copolymer with ethylene content of 35 mol% and melting point of 177℃ Substance (A-7) (manufactured by Kuraray Co., Ltd., trade name EVAL C109B) 17.5% by weight The obtained press sheet was subjected to a tensile test and an impact test. The evaluation results are shown in Table 5. show.

[0124] Comparative Example 8 As the thermoplastic resin (A-8) instead of the ethylene-vinyl acetate copolymer composition (B), Density 923kg / m 3Low density polyethylene with a melt mass flow rate of 4g / 10min and a melting point of 109℃ The only exception was the use of 30% by weight of polyethylene (trade name Petrothene 217, manufactured by Tosoh Corporation). A press sheet was obtained in the same manner as in Example 17.

[0125] The obtained press sheet was subjected to a tensile test and an impact test. The evaluation results are shown in Table 5. show.

[0126] Comparative Example 9 Ethylene-vinyl acetate copolymer composition (B) 30% by weight of vinyl acetate content 80% by weight %, and a melt mass flow rate of 5 g / 10 min. 0) (trade name: Levaprene 800, manufactured by Lanxess KK) was used in an amount of 30% by weight. Press sheets were obtained using the same method as in 17.

[0127] The obtained press sheet was subjected to a tensile test and an impact test. The evaluation results are shown in Table 5. show.

[0128] [Table 5]

[0129] Example 19 As the thermoplastic resin (A), a 25 μm thick polyethylene film and a 12 μm thick polyethylene film were used. Used multilayer film (A) in which polyethylene terephthalate film was laminated with an adhesive. -Rc) was 70% by weight, and the ethylene-vinyl acetate copolymer composition (B) was the ethylene-vinyl acetate copolymer composition having the following composition: 30% by weight of ethylene-vinyl acetate copolymer was used. [Thermoplastic resin (A-Rc)] PE 40.7% by weight, melt mass flow rate 8g / 10min, melting point 105℃ Low-density polyethylene (manufactured by Tosoh Corporation, product name Petrothene 203) Adhesive 0.2% by weight, isocyanate anchor coating agent (Mitsui Chemicals, Inc.) Product name: Takelac A-3210) and isocyanate anchor coating agent (Mitsui Chemicals Co., Ltd.) A mixture obtained by mixing two cellulose acetate copolymers (manufactured by Takenate Co., Ltd., product name: Takenate A-3072) in a ratio of 3:1 PET 29.1% by weight (Toyobo, product name Ester Film E5100) [Ethylene-vinyl acetate copolymer composition (B)] Ethylene vinyl acetate content 25% by weight, melt mass flow rate 3g / 10min Vinyl acetate copolymer (B-25) (Tosoh Corporation, product name Ultrathene 640) 15 layers amount% Ethylene with a vinyl acetate content of 50% by weight and a melt mass flow rate of 3 g / 10 min Vinyl acetate copolymer (B-50) (Levaprene 500, manufactured by Lanxess KK) 7. 5% by weight Ethylene vinyl acetate content 80% by weight, melt mass flow rate 5g / 10min Vinyl acetate copolymer (B-80) (Levaprene 800, manufactured by Lanxess KK) 7. 5% by weight Cut the multilayer film (A-Rc) into approximately 5mm squares, which is the size that can be fed into the extruder. The extrusion was performed using a Labo Plastomill (Toyo Seiki Co., Ltd.) equipped with a twin-screw extruder 2D25-S (Toyo Seiki Co., Ltd.). Using a screw (manufactured by Yosei Seiki), the resin was melt-kneaded at a resin temperature of 270°C and a screw rotation speed of 60 rpm. Thus, a pellet-shaped resin composition for multilayer film (A-Rc) was obtained.

[0130] Multilayer film (A-Rc) 70% by weight of resin composition and ethylene- 30% by weight of vinyl acetate copolymer composition (B) was dry-blended and extruded in a twin-screw extruder 2D25- The trees were grown using a Labo Plastomill (manufactured by Toyo Seiki Co., Ltd.) equipped with a 1000-kJ PET bottle (manufactured by Toyo Seiki Co., Ltd.). The mixture was melt-kneaded at a temperature of 230°C and a rotation speed of 60 rpm to obtain a pellet-shaped resin composition. .

[0131] The obtained resin composition pellets were molded in a press molding machine (AWFA-50 model, manufactured by Shinto Metal Industries Co., Ltd.). ) using a pressure of 10 MPa, a heating temperature of 200°C (primary pressure x 3 minutes, secondary pressure x 3 minutes), The mixture was press-molded at a cooling temperature of 25°C (4 minutes) to obtain a pressed sheet with a thickness of 0.1 mm. .

[0132] The obtained press sheet was subjected to a tensile test and an impact test. The evaluation results are shown in Table 6. show.

[0133] Example 20 The same procedure was carried out except that the composition of 30% by weight of the ethylene-vinyl acetate copolymer composition (B) was as follows: A pressed sheet was obtained in the same manner as in Example 19.

[0134] Ethylene vinyl acetate content 25% by weight, melt mass flow rate 3g / 10min Vinyl acetate copolymer (B-25) (manufactured by Tosoh Corporation, trade name Ultrathene 640) 9 weight % Ethylene with a vinyl acetate content of 40% by weight and a melt mass flow rate of 3 g / 10 min Vinyl acetate copolymer (B-40) (manufactured by LANXESS KK, trade name Levaprene 400) 4-ply amount% Ethylene with a vinyl acetate content of 50% by weight and a melt mass flow rate of 3 g / 10 min Vinyl acetate copolymer (B-50) (manufactured by LANXESS KK, trade name Levaprene 500) 6-ply amount% Ethylene vinyl acetate content 70% by weight, melt mass flow rate 5g / 10min Vinyl acetate copolymer (B-70) (manufactured by LANXESS KK, trade name Levaprene 700) triple layer amount% Ethylene vinyl acetate content 80% by weight, melt mass flow rate 5g / 10min Vinyl acetate copolymer (B-80) (manufactured by LANXESS KK, trade name Levaprene 800) 8 layers amount% The obtained press sheet was subjected to a tensile test and an impact test. The evaluation results are shown in Table 6. show.

[0135] Comparative Example 10 As the thermoplastic resin (A), only 100% by weight of the multilayer film (A-Rc) was used.

[0136] The multilayer film (A-Rc) is cut to a size that can be fed into the extruder, and then extruded into the twin-screw extruder 2D2. Using a Labo Plastomill (manufactured by Toyo Seiki Co., Ltd.) equipped with a 5-S (manufactured by Toyo Seiki Co., Ltd.) The resin was melt-kneaded at a resin temperature of 270°C and a screw rotation speed of 60 rpm, and pelletized into multilayer A film (A-Rc) resin composition was obtained.

[0137] The obtained resin composition pellets were molded in a press molding machine (AWFA-50 manufactured by Shinto Metal Industries Co., Ltd.). Using a pressure of 10 MPa, heating temperature of 200°C (primary pressure x 3 minutes, secondary pressure x 3 minutes), cooling The mixture was press-molded at a cooling temperature of 25°C (4 minutes) to obtain a pressed sheet with a thickness of 0.1 mm.

[0138] The obtained press sheet was subjected to a tensile test and an impact test. The evaluation results are shown in Table 6. show.

[0139] [Table 6]

[0140] Example 21 The thermoplastic resin (A) is 70% by weight of a thermoplastic resin composition having the following composition, and ethylene - As the vinyl acetate copolymer composition (B), ethylene-vinyl acetate copolymer 30% of the following composition was used. Weight percent was used. [Thermoplastic resin (A) composition] High density polyethylene with a melt mass flow rate of 5.5g / 10min and a melting point of 133℃ (A-4) (Tosoh Corporation, product name Nipolon HD4020) 49% by weight Polypropylene (A) with a melt mass flow rate of 6.5 g / 10 min and a melting point of 137°C -5) (Novatec PP FW4BT, manufactured by Japan Polypropylene Corporation) 7% by weight PETG resin (A-6) (manufactured by Eastman Chemical Co.) with a glass transition temperature of 67°C Product name Eastar GN5011) 7% by weight Ethylene-vinyl alcohol copolymer with ethylene content of 35 mol% and melting point of 177℃ Substance (A-7) (manufactured by Kuraray Co., Ltd., trade name EVAL C109B) 7% by weight [Ethylene-vinyl acetate copolymer composition (B)] Ethylene vinyl acetate content 25% by weight, melt mass flow rate 3g / 10min Vinyl acetate copolymer (B-25) (Tosoh Corporation, product name Ultrathene 640) 15 layers amount% Ethylene with a vinyl acetate content of 50% by weight and a melt mass flow rate of 3 g / 10 min Vinyl acetate copolymer (B-50) (Levaprene 500, manufactured by Lanxess KK) 7. 5% by weight Ethylene vinyl acetate content 80% by weight, melt mass flow rate 5g / 10min Vinyl acetate copolymer (B-80) (Levaprene 800, manufactured by Lanxess KK) 7. 5% by weight Thermoplastic resins (A-4) to (A-7) and an ethylene-vinyl acetate copolymer composition (B) Dry blending was carried out using a twin-screw extruder (manufactured by Technovel, product name UL) with a screw diameter of 25 mm. Using a Tnano25TW), the resin temperature was 200°C and the screw rotation speed was 100 rpm. The mixture was melt-kneaded at 100°C to obtain a resin composition.

[0141] The obtained resin composition was pressed using a press molding machine (AWFA-50 manufactured by Shinto Metal Industries Co., Ltd.). Pressure: 10 MPa, heating temperature: 200°C (primary pressure x 3 minutes, secondary pressure x 3 minutes), cooling temperature: The mixture was press-molded at 25°C (4 minutes) to obtain a pressed sheet with a thickness of 0.1 mm.

[0142] The obtained press sheet was subjected to a tensile test and an impact test. The evaluation results are shown in Table 7. show.

[0143] Example 22 The same procedure as in Example 21 was used except that the screw rotation speed of the twin-screw extruder was set to 600 rpm. More press sheets were obtained.

[0144] The obtained press sheet was subjected to a tensile test and an impact test. The evaluation results are shown in Table 7. show.

[0145] Comparative Example 11 The thermoplastic resin (A) was 100% by weight of a thermoplastic resin composition having the following composition: A press sheet was obtained in the same manner as in Example 22. [Thermoplastic resin (A) composition] High-density polyethylene with a melt mass flow rate of 5.5g / 10min and a melting point of 133℃ (A-4) (Tosoh Corporation, product name Nipolon HD4020) 70% by weight Polypropylene (A) with a melt mass flow rate of 6.5 g / 10 min and a melting point of 137°C -5) (Novatec PP FW4BT, manufactured by Japan Polypropylene Corporation) 10% by weight PETG resin (A-6) (manufactured by Eastman Chemical Company) with a glass transition temperature of 67°C Product name Eastar GN5011) 10% by weight Ethylene-vinyl alcohol copolymer with ethylene content of 35 mol% and melting point of 177℃ Substance (A-7) (manufactured by Kuraray Co., Ltd., product name EVAL C109B) 10% by weight The obtained press sheet was subjected to a tensile test and an impact test. The evaluation results are shown in Table 7. show.

[0146] [Table 7] [Industrial Applicability]

[0147] Molded articles made from the resin composition of the present invention are useful for automobile parts, housings for electric and electronic parts, building materials, soil It can be used for a variety of purposes, including wood materials, agricultural materials, containers, packaging materials, adhesives, and daily necessities. do.

Claims

1. The impact modifier for at least one thermoplastic resin selected from the group consisting of polyolefin resins, acrylic acid resins, polyamide resins, polyester resins, polycarbonate resins, polystyrene resins, and styrene-acrylonitrile copolymers comprises a composition containing the following three or more types of ethylene-vinyl acetate copolymers having different vinyl acetate contents: - Ethylene-vinyl acetate copolymer 1 having a vinyl acetate content of 15% by weight or more and 30% by weight or less; - Ethylene-vinyl acetate copolymer 2 having a vinyl acetate content of 45% by weight or more and 55% by weight or less; and Ethylene-vinyl acetate copolymer 3 having a vinyl acetate content of 75% by weight or more and 85% by weight or less.

2. An impact modifier as described in claim 1, which can be used for recycling by compatibilizing at least two types of resin selected from the group consisting of polyolefin resins, acrylic acid resins, polyamide resins, polyester resins, polycarbonate resins, polystyrene resins, and styrene-acrylonitrile copolymers.

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