Thermoplastic resin composition

Abstract

Provided is a thermoplastic resin composition containing a thermoplastic resin and an impact resistance improver and capable of exhibiting excellent impact resistance even when containing an additive such as a filler or a softener.　The thermoplastic resin composition according to an embodiment of the present invention contains a thermoplastic resin and an impact resistance improver. The impact resistance improver contains a rubber component-containing foam material.

Description

thermoplastic resin composition

[0001] The present invention relates to a thermoplastic resin composition.

[0002] Thermoplastic resins are combined with other suitable components to form thermoplastic resin compositions, which are used in a variety of applications.

[0003] BACKGROUND ART Thermoplastic resin compositions containing impact modifiers are known as thermoplastic resin compositions having excellent impact resistance.

[0004] Impact modifiers used in such thermoplastic resin compositions having excellent impact resistance include, for example, rubber components such as ethylene-propylene-diene rubber (EPDM) (see, for example, Patent Documents 1 and 2), and core-shell organic impact modifier additives (see, for example, Patent Document 3).

[0005] JP-A No. 5-1185 JP-A No. 7-118488 Special Publication No. 2009-515003

[0006] Rubber components such as ethylene-propylene-diene rubber (EPDM) and its vulcanizates are generally provided in the form of rubber-based compounding materials blended with additives such as fillers and softeners. Therefore, considering the use of such rubber-based compounding materials as impact modifiers for thermoplastic resins, thermoplastic resin compositions containing thermoplastic resins and rubber-based compounding materials were prepared. However, it was found that thermoplastic resin compositions containing such rubber-based compounding materials had lower impact resistance than thermoplastic resin compositions containing ordinary rubber components. The inventors then speculated that this lower impact resistance was due to the presence of additives such as fillers and softeners contained in the rubber-based compounding materials in the thermoplastic resin compositions containing thermoplastic resins and rubber components.

[0007] An object of the present invention is to provide a thermoplastic resin composition containing a thermoplastic resin and an impact resistance modifier, which is capable of exhibiting excellent impact resistance even when it contains additives such as a filler and a softener.

[0008] The present inventors have conducted extensive research into means for solving the above problems, and as a result have found that even if a thermoplastic resin composition containing a thermoplastic resin and an impact modifier contains additives such as a filler or a softener, excellent impact resistance can be achieved by using a foamed rubber component-containing foamed material as the impact modifier.

[0009] [1] A thermoplastic resin composition according to an embodiment of the present invention is a thermoplastic resin composition containing a thermoplastic resin and an impact modifier, wherein the impact modifier contains a rubber-containing foam material. [2] In the thermoplastic resin composition described in [1] above, the thermoplastic resin may be at least one selected from the group consisting of olefin-based resins and styrene-based resins. [3] In the thermoplastic resin composition described in [1] or [2] above, the rubber-containing foam material may contain a vulcanizate of ethylene-propylene-diene rubber. [4] In the thermoplastic resin composition described in any one of [1] to [3] above, the rubber-containing foam material may be a waste material. [5] The thermoplastic resin composition described in any one of [1] to [4] above may contain an inorganic material. [6] The thermoplastic resin composition described in any one of [1] to [5] above may be used for outdoor building materials.

[0010] According to the present invention, it is possible to provide a thermoplastic resin composition containing a thermoplastic resin and an impact resistance modifier, which can exhibit excellent impact resistance even when it contains additives such as a filler or a softener.

[0011] [Terminology] In this specification, when the expression "weight" appears, it may be read as "mass," which is commonly used as an SI unit indicating weight, and vice versa.

[0012] In this specification, the expression "(meth)acrylic" means "acrylic and / or methacrylic", the expression "(meth)acrylate" means "acrylate and / or methacrylate", the expression "(meth)allyl" means "allyl and / or methallyl", and the expression "(meth)acrolein" means "acrolein and / or methacrolein".

[0013] <<1. Thermoplastic Resin Composition>> A thermoplastic resin composition according to an embodiment of the present invention comprises a thermoplastic resin and an impact modifier, and the impact modifier comprises a rubber-containing foam material. By including a foamed rubber-containing foam material as the impact modifier, the thermoplastic resin composition according to an embodiment of the present invention can exhibit excellent impact resistance even when the thermoplastic resin composition contains additives such as a filler or a softener. If the impact modifier is solely a non-foamed material, the effects of the present invention may not be achieved.

[0014] As described above, the thermoplastic resin composition according to an embodiment of the present invention can exhibit excellent impact resistance even when it contains additives such as a filler or a softener, but it can also exhibit excellent impact resistance even when it does not contain additives such as a filler or a softener.

[0015] The thermoplastic resin composition according to the embodiment of the present invention can exhibit excellent impact resistance.

[0016] The thermoplastic resin composition according to an embodiment of the present invention preferably has an extrusion molding Charpy impact strength of 4.8 kJ / m or less when a material molded by an extrusion molding machine is cut into a flat plate, the flat plate is processed to prepare a test piece (notched) for measuring Charpy impact strength in accordance with JIS K 7111-1, and a Charpy impact test is performed in accordance with JIS K 7111-1. 2 More preferably, 5.0 kJ / m 2 More preferably, it is 5.2 kJ / m or more. 2 More preferably, it is 5.4 kJ / m or more. 2 More preferably, it is 5.6 kJ / m or more. 2More preferably, it is 5.8 kJ / m or more. 2 More preferably, it is 6.0 kJ / m or more. 2 The higher the extrusion molding Charpy impact strength, the better, but in reality, it is, for example, 25 kJ / m 2 The following is the result.

[0017] The thermoplastic resin composition according to an embodiment of the present invention preferably has an injection molding Charpy impact strength of 4.8 kJ / m when a test piece (notched) for measuring Charpy impact strength is prepared in accordance with JIS K 7111-1 using an injection molding machine and a Charpy impact test is carried out in accordance with JIS K 7111-1. 2 More preferably, 5.0 kJ / m 2 More preferably, it is 5.2 kJ / m or more. 2 More preferably, it is 5.4 kJ / m or more. 2 More preferably, it is 5.6 kJ / m or more. 2 More preferably, it is 5.8 kJ / m or more. 2 More preferably, it is 6.0 kJ / m or more. 2 The higher the injection molding Charpy impact strength, the better, but in reality, it is, for example, 25 kJ / m 2 The following is the result.

[0018] The total content of the thermoplastic resin and the impact modifier in the thermoplastic resin composition according to an embodiment of the present invention may be any appropriate content ratio as long as the effects of the present invention are not impaired. In terms of further exhibiting the effects of the present invention, the total content of the thermoplastic resin and the impact modifier in the thermoplastic resin composition according to an embodiment of the present invention may be, for example, 10% by weight to 100% by weight, 20% by weight to 90% by weight, 30% by weight to 80% by weight, 35% by weight to 75% by weight, 40% by weight to 70% by weight, 45% by weight to 65% by weight, or 50% by weight to 60% by weight.

[0019] The thermoplastic resin composition according to the embodiment of the present invention can be produced by any suitable method as long as the effects of the present invention are not impaired. Examples of such a production method include a method in which the constituent components (the thermoplastic resin, the impact modifier, and, if necessary, other components) are mixed by any suitable means.

[0020] <1-1. Thermoplastic Resin> Any appropriate thermoplastic resin can be used as the thermoplastic resin as long as it does not impair the effects of the present invention. The thermoplastic resin may be one type or two or more types. Examples of such thermoplastic resins include polyolefin-based resins such as polyethylene, polypropylene, and cyclic cycloolefin resins; polystyrene-based resins such as polystyrene, acrylonitrile-styrene copolymer (AS resin), and acrylonitrile-butadiene-styrene copolymer (ABS resin); polyester-based resins such as polyethylene terephthalate and polybutylene terephthalate; polyamide-based resins; polycarbonate-based resins; polyacetal-based resins; polyimide-based resins; polyetherimide-based resins; polyurethane-based resins; polyphenylene ether-based resins; polyphenylene sulfide-based resins; polysulfone-based resins; and acrylic-based resins. At least one selected from the group consisting of polyolefin-based resins and polystyrene-based resins is preferred.

[0021] The content of the thermoplastic resin in the thermoplastic resin composition according to an embodiment of the present invention may be any appropriate content ratio as long as the effects of the present invention are not impaired. In terms of being able to further exhibit the effects of the present invention, the content of the thermoplastic resin in the thermoplastic resin composition according to an embodiment of the present invention is, for example, 10% by weight to 90% by weight, 20% by weight to 80% by weight, 25% by weight to 70% by weight, 30% by weight to 65% by weight, 35% by weight to 60% by weight, or 40% by weight to 55% by weight.

[0022] <1-2. Impact Modifier> The thermoplastic resin composition according to an embodiment of the present invention contains an impact modifier. The impact modifier may be of one type or two or more types.

[0023] The content of the impact modifier in the thermoplastic resin composition according to an embodiment of the present invention may be any appropriate content ratio as long as the effects of the present invention are not impaired. In terms of being able to further exhibit the effects of the present invention, the content of the impact modifier in the thermoplastic resin composition according to an embodiment of the present invention is, for example, 1% by weight to 50% by weight, alternatively, 2% by weight to 40% by weight, 3% by weight to 30% by weight, 4% by weight to 20% by weight, or 5% by weight to 15% by weight.

[0024] The content of the impact modifier in the thermoplastic resin composition according to an embodiment of the present invention is, for example, 1 to 60 parts by weight, alternatively 5 to 50 parts by weight, alternatively 8 to 40 parts by weight, or alternatively 10 to 30 parts by weight, relative to 100 parts by weight of the thermoplastic resin in the thermoplastic resin composition according to an embodiment of the present invention, in order to further exhibit the effects of the present invention.

[0025] The impact resistance modifier may be in the form of a pulverized product, in order to more effectively exhibit the effects of the present invention.

[0026] <1-2-a. Rubber-Containing Foamed Material> The impact modifier included in the thermoplastic resin composition according to an embodiment of the present invention contains a rubber-containing foamed material, which is a foam. By including a rubber-containing foamed material in the impact modifier, the thermoplastic resin composition according to an embodiment of the present invention can exhibit excellent impact resistance even when it contains additives such as a filler or a softener.

[0027] The content of the rubber component-containing foam material in the impact modifier may be any appropriate content ratio as long as the effects of the present invention are not impaired. In order to further exhibit the effects of the present invention, the content of the rubber component-containing foam material in the impact modifier is, for example, 50% by weight to 100% by weight, or may be 60% by weight to 100% by weight, 70% by weight to 100% by weight, 80% by weight to 100% by weight, 90% by weight to 100% by weight, 95% by weight to 100% by weight, or 98% by weight to 100% by weight.

[0028] The volume expansion ratio (ratio of density before and after expansion) of the rubber component-containing foamed material is, for example, 2 times or more, may be 2 to 30 times, or may be 5 to 30 times.

[0029] The apparent density of the rubber component-containing foam material (apparent density according to JIS K 6767) is, for example, 0.04 g / cm 3 ~0.5g / cm 3 and 0.04 g / cm 3 ~0.3g / cm 3 may be.

[0030] The cell diameter of the rubber component-containing foamed material is, for example, 300 μm to 1200 μm, and may be 300 μm to 1000 μm.

[0031] The rubber component-containing foam material contains a rubber component. Any appropriate rubber component can be used as the rubber component contained in the rubber component-containing foam material as long as the effects of the present invention are not impaired. The rubber component may be one type or two or more types. From the viewpoint of further exhibiting the effects of the present invention, examples of the rubber component contained in the rubber component-containing foam material include ethylene-propylene-diene rubber (EPDM), ethylene-propylene rubber (EPM), ethylene-vinyl acetate rubber (EVA), nitrile rubber (NBR), silicone rubber, fluororubber, urethane rubber, acrylic rubber, isoprene rubber (IR), styrene-butadiene rubber (SBR), butadiene rubber (BR), butyl rubber (IIR), chloroprene rubber, vulcanizates of these rubbers, and core-shell impact resistance additives. One preferred rubber component contained in the rubber component-containing foam material is a vulcanizate of ethylene-propylene-diene rubber (EPDM).

[0032] Ethylene-propylene-diene rubber (EPDM) is a rubber obtained by copolymerizing ethylene, propylene, and a diene. By further copolymerizing a diene into the ethylene-propylene copolymer to introduce unsaturated bonds, it can be vulcanized with a vulcanizing agent.

[0033] As the diene, any appropriate diene can be used as long as it does not impair the effects of the present invention. Only one diene may be used, or two or more dienes may be used. In terms of further exhibiting the effects of the present invention, examples of dienes that can be used include 5-ethylidene-2-norbornene, 1,4-hexadiene, and dicyclopentadiene.

[0034] The diene content in the ethylene propylene diene rubber (EPDM) is, for example, 1% by weight to 20% by weight, and may be 3% by weight to 10% by weight.

[0035] The content of the rubber component in the rubber component-containing foamed material may be any appropriate content ratio as long as the effects of the present invention are not impaired. In terms of further exhibiting the effects of the present invention, the content of the rubber component in the rubber component-containing foamed material is, for example, 1% by weight to 100% by weight, 5% by weight to 70% by weight, 10% by weight to 50% by weight, 13% by weight to 40% by weight, or 15% by weight to 35% by weight.

[0036] The rubber component-containing foamed material may contain a filler. The filler may be one type or two or more types. In terms of further exhibiting the effects of the present invention, examples of the filler include inorganic fillers such as calcium carbonate (e.g., heavy calcium carbonate), magnesium carbonate, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, silicic acid and its salts, clay, talc, mica powder, bentonite, silica, alumina, aluminum silicate, acetylene black, and aluminum powder; organic fillers such as cork; and other known fillers. Inorganic fillers are preferred, and calcium carbonate is more preferred.

[0037] The content of the filler in the rubber component-containing foamed material may be any appropriate content ratio as long as the effects of the present invention are not impaired. In order to further exhibit the effects of the present invention, the content of the filler in the rubber component-containing foamed material is, for example, 300 parts by weight or less, or may be 10 to 300 parts by weight, 30 to 200 parts by weight, 50 to 150 parts by weight, or 70 to 130 parts by weight, relative to 100 parts by weight of the rubber component.

[0038] When the rubber component-containing foamed material contains a filler, the thermoplastic resin composition according to the embodiment of the present invention may consequently contain the filler. However, even when the thermoplastic resin composition according to the embodiment of the present invention contains such a filler, it can exhibit excellent impact resistance by using the rubber component-containing foamed material, which is a foam, as an impact modifier.

[0039] The rubber component-containing foamed material may contain a softener. The softener may be of only one type, or two or more types. In terms of further exhibiting the effects of the present invention, examples of softeners include drying oils, animal and vegetable oils (e.g., linseed oil), paraffin, asphalt, petroleum oils (e.g., paraffinic process oil, naphthenic process oil, aromatic process oil), low-molecular-weight polymers, organic acid esters (e.g., phthalate esters (e.g., di-2-ethylhexyl phthalate (DOP) and dibutyl phthalate (DBP)), phosphate esters, higher fatty acid esters, and alkylsulfonic acid esters), and thickeners. Paraffin, asphalt, and petroleum oils are preferred.

[0040] The content of the softener in the rubber component-containing foamed material may be any appropriate content ratio as long as the effects of the present invention are not impaired. In terms of further exhibiting the effects of the present invention, the content of the softener in the rubber component-containing foamed material is, for example, 500 parts by weight or less, or may be 10 to 400 parts by weight, 30 to 300 parts by weight, 50 to 250 parts by weight, 70 to 220 parts by weight, or 100 to 200 parts by weight, relative to 100 parts by weight of the rubber component.

[0041] When the rubber component-containing foam material contains a softener, the thermoplastic resin composition according to the embodiment of the present invention may consequently contain the softener. However, even when the thermoplastic resin composition according to the embodiment of the present invention contains such a softener, it can exhibit excellent impact resistance by using the rubber component-containing foam material, which is a foam, as an impact modifier.

[0042] As the rubber component-containing foam material, for example, an EPDM foam described in Japanese Patent No. 5420386 may be used. Alternatively, as the rubber component-containing foam material, a commercially available product may be used.

[0043] The rubber component-containing foam material may be a waste material. The waste material may be waste generated during the production of the rubber component-containing foam material, or may be a recovered product of a used rubber component-containing foam material. If a waste material can be used as the rubber component-containing foam material, this is preferable because it can contribute to reducing the environmental load.

[0044] <1-2-b. Preparation of Rubber-Containing Foamed Material> The rubber-containing foamed material can be prepared by any appropriate method as long as the effects of the present invention are not impaired. For example, the rubber-containing foamed material can be formed by foaming a foaming composition containing a rubber component and a foaming material.

[0045] The rubber component that can be contained in the foaming composition may be the same as that contained in the rubber component-containing foam material. Note that, when the foaming composition contains a vulcanizing agent, the rubber component that can be contained in the foaming composition does not need to be a vulcanizate.

[0046] As the foaming agent that can be contained in the foam composition, any appropriate foaming agent can be adopted as long as the effects of the present invention are not impaired. The foaming agent may be one type only or two or more types. Examples of such foaming agents include organic foaming agents and inorganic foaming agents, and organic foaming agents are preferred.

[0047] Examples of organic blowing agents include azo compounds such as azodicarbonamide (ADCA), barium azodicarboxylate, azobisisobutyronitrile (AIBN), azocyclohexylnitrile, and azodiaminobenzene; 4,4'-oxybis(benzenesulfonylhydrazide) (OBSH), paratoluenesulfonylhydrazide, diphenylsulfone-3,3'-disulfonylhydrazide, 2,4-toluenedisulfonylhydrazide, p,p-bis(benzenesulfonylhydrazide) ether, and benzene-1, Examples include hydrazide compounds such as 3-disulfonylhydrazide and allylbis(sulfonylhydrazide); semicarbazide compounds such as p-toluylenesulfonylsemicarbazide and 4,4'-oxybis(benzenesulfonylsemicarbazide); fluorinated alkanes such as trichloromonofluoromethane and dichloromonofluoromethane; and triazole compounds such as 5-morpholyl-1,2,3,4-thiatriazole; and preferably, azo compounds, and more preferably, azodicarbonamide (ADCA).

[0048] Examples of inorganic foaming agents include hydrogen carbonates such as sodium hydrogen carbonate and ammonium hydrogen carbonate; carbonates such as sodium carbonate and ammonium carbonate; nitrites such as sodium nitrite and ammonium nitrite; borohydrides such as sodium borohydride; and azides.

[0049] Organic foaming agents include thermally expandable microparticles in which a thermally expandable substance is encapsulated in microcapsules. Commercially available products of such thermally expandable microparticles include, for example, the product name "Microsphere" (manufactured by Matsumoto Yushi Co., Ltd.).

[0050] The content of the foaming agent in the foam composition is, for example, 1 to 30 parts by weight, or may be 5 to 25 parts by weight, based on 100 parts by weight of the rubber component.

[0051] The foaming composition may contain a foaming aid. Any appropriate foaming aid may be used as the foaming aid as long as the effects of the present invention are not impaired. The foaming aid may be one type or two or more types. Examples of such foaming aids include urea-based compounds, salicylic acid-based compounds, and benzoic acid-based compounds, and urea-based compounds are preferred.

[0052] The content of the foaming aid in the foaming composition is, for example, 20 parts by weight or less, or may be 1 to 15 parts by weight, or may be 2 to 10 parts by weight, relative to 100 parts by weight of the rubber component.

[0053] The foam composition may contain a vulcanizing agent. When the foam composition contains a vulcanizing agent, the rubber component-containing foam material formed by foaming may contain a vulcanizate of the rubber component. For example, when the rubber component is ethylene propylene diene rubber (EPDM), the rubber component-containing foam material may contain a vulcanizate of ethylene propylene diene rubber.

[0054] Any appropriate vulcanizing agent can be used as the vulcanizing agent as long as it does not impair the effects of the present invention. The vulcanizing agent may be one type or two or more types. Examples of such vulcanizing agents include sulfur, selenium, magnesium oxide, lead monoxide, organic peroxides (e.g., cumene peroxide, etc.), polyamines, oximes (e.g., p-quinone dioxime, p,p'-dibenzoylquinone dioxime, etc.), nitroso compounds (e.g., p-dinitrosobenzine, etc.), resins (e.g., alkylphenol-formaldehyde resin, melamine-formaldehyde condensate, etc.), and ammonium salts (e.g., ammonium benzoate, etc.). From the viewpoint of the durability of the vulcanized product of the rubber component that can be obtained, sulfur is preferred.

[0055] The content of the vulcanizing agent in the foaming composition can be appropriately set depending on the type of vulcanizing agent within a range that does not impair the effects of the present invention. For example, when the vulcanizing agent is sulfur, the content is, for example, 10 parts by weight or less, or may be 0.1 to 5 parts by weight, or may be 0.5 to 3 parts by weight, per 100 parts by weight of the rubber component.

[0056] The foamable composition may contain a vulcanization accelerator. Any appropriate foaming aid may be used as the vulcanization accelerator as long as the effects of the present invention are not impaired. The vulcanization accelerator may be one type only, or two or more types. Examples of such vulcanization accelerators include thiourea-based vulcanization accelerators, thiazole-based vulcanization accelerators, dithiocarbamic acid-based vulcanization accelerators, and thiuram-based vulcanization accelerators. As the vulcanization accelerators, four types of thiourea-based vulcanization accelerators, thiazole-based vulcanization accelerators, dithiocarbamic acid-based vulcanization accelerators, and thiuram-based vulcanization accelerators may be used in combination. In such a combined use, the weight ratio of the thiourea-based vulcanization accelerator / thiazole-based vulcanization accelerator / dithiocarbamic acid-based vulcanization accelerator / thiuram-based vulcanization accelerator is, for example, (1-20) / (1-20) / (1-20) / (1-30), or may be (1-15) / (1-10) / (1-10) / (1-30), or may be (2-15) / (2-7) / (1-5) / (1-25).

[0057] Examples of thiourea vulcanization accelerators include N,N'-diethylthiourea, N,N'-dibutylthiourea, N,N'-diphenylthiourea, and trimethylthiourea. Examples of thiazole vulcanization accelerators include 2-mercaptobenzothiazole, zinc salt of 2-mercaptobenzothiazole, cyclohexylamine salt of 2-mercaptobenzothiazole, and dibenzothiazyl disulfide. Examples of dithiocarbamic acid vulcanization accelerators include zinc diisononyldithiocarbamate and zinc dibenzyldithiocarbamate. Examples of thiuram vulcanization accelerators include tetrakis(2-ethylhexyl)thiuram disulfide and tetrabenzylthiuram disulfide.

[0058] The content ratio of the vulcanization accelerator in the foaming composition is, for example, 20 parts by weight or less, or may be 0.1 to 10 parts by weight, or may be 1 to 7 parts by weight, relative to 100 parts by weight of the rubber component.

[0059] The foaming composition may contain a vulcanization aid. Any appropriate vulcanization aid may be used as the vulcanization aid as long as the effects of the present invention are not impaired. The vulcanization aid may be one type or two or more types. An example of such a vulcanization aid is zinc oxide.

[0060] The content ratio of the vulcanization aid in the foaming composition is, for example, 30 parts by weight or less, or may be 1 to 20 parts by weight, or may be 2 to 10 parts by weight, relative to 100 parts by weight of the rubber component.

[0061] The foam composition may contain a filler. When the foam composition contains a filler, the rubber component-containing foam material formed by foaming may contain the filler.

[0062] As for the filler that can be contained in the foam composition, the above-mentioned explanation of the filler contained in the rubber component-containing foam material can be applied.

[0063] The foam composition may contain a softener. When the foam composition contains a softener, the rubber component-containing foam material formed by foaming may contain the softener.

[0064] The softener that can be contained in the foam composition may be the same as that described above for the softener contained in the rubber component-containing foam material.

[0065] The foaming composition may contain a lubricant. Any appropriate lubricant may be used as the lubricant as long as it does not impair the effects of the present invention. The lubricant may be one type or two or more types. Examples of such lubricants include stearic acid and its esters.

[0066] The content of the lubricant in the foam composition is, for example, 10 parts by weight or less, or may be 0.5 to 5 parts by weight, or may be 1 to 5 parts by weight, relative to 100 parts by weight of the rubber component.

[0067] The foamable composition may contain a pigment. Any appropriate pigment may be used as the pigment as long as the effects of the present invention are not impaired. The pigment may be one type only, or two or more types. An example of such a pigment is carbon black.

[0068] The content of the pigment in the foaming composition is, for example, 100 parts by weight or less, or may be 0.1 to 80 parts by weight, or may be 0.5 to 50 parts by weight, relative to 100 parts by weight of the rubber component.

[0069] The foam composition may contain other components, as needed, to the extent that the effects of the present invention are not impaired. Examples of such other components include plasticizers, antioxidants, antioxidants, colorants, mildew inhibitors, and flame retardants.

[0070] As a method for forming a rubber component-containing foam material by foaming a foaming composition, any appropriate method can be adopted as long as the effects of the present invention are not impaired. Such a method includes, for example, a preparation step of preparing a foaming composition, a molding step of extruding the prepared foaming composition into a sheet or the like using an extruder, and a foaming step of heating the extruded foaming composition to vulcanize and foam it.

[0071] In the preparation step, the components of the foaming composition are blended and kneaded to form a foaming composition. In the preparation step, the kneading may be performed while appropriately heating. In the preparation step, for example, components other than the vulcanizing agent, vulcanization accelerator, foaming agent, and foaming aid are first kneaded to prepare a primary mixture, and then the vulcanizing agent, vulcanization accelerator, foaming agent, and foaming aid are added to the primary mixture and kneaded to prepare a foaming composition (secondary mixture). In addition, when preparing the primary mixture, a portion of the vulcanization accelerator (for example, a thiourea-based vulcanization accelerator) may also be blended.

[0072] As the molding conditions in the molding step and the heating conditions in the foaming step, any appropriate conditions can be adopted as long as the effects of the present invention are not impaired.

[0073] <1-2-c. Other Impact Modifiers> The impact modifier may include an impact modifier other than the rubber component-containing foamed material. The other impact modifier may be a single type or two or more types. As such an impact modifier, any appropriate impact modifier other than the rubber component-containing foamed material may be used as long as it does not impair the effects of the present invention. Examples of such an impact modifier include known non-foamed rubber components, such as ethylene-propylene-diene rubber (EPDM), ethylene-propylene rubber (EPM), ethylene-vinyl acetate rubber (EVA), nitrile rubber (NBR), silicone rubber, fluororubber, urethane rubber, acrylic rubber, isoprene rubber (IR), styrene-butadiene rubber (SBR), butadiene rubber (BR), butyl rubber (IIR), chloroprene rubber, vulcanizates of these rubbers, and core-shell impact additives.

[0074] The content ratio of the other impact modifier in the impact modifier is, for example, 50% by weight or less, may be 0% by weight to 40% by weight, 0% by weight to 30% by weight, 0% by weight to 20% by weight, 0% by weight to 10% by weight, 0% by weight to 5% by weight, or 0% by weight to 2% by weight, in order to further exhibit the effects of the present invention.

[0075] <1-3. Inorganic Substance> The thermoplastic resin composition according to an embodiment of the present invention may contain an inorganic substance from the viewpoint of further exhibiting the effects of the present invention. In this case, the total content ratio of the thermoplastic resin, the inorganic substance, and the impact modifier in the thermoplastic resin composition according to an embodiment of the present invention may be any appropriate content ratio as long as the effects of the present invention are not impaired. In terms of further exhibiting the effects of the present invention, the total content ratio of the thermoplastic resin, the inorganic substance, and the impact modifier in the thermoplastic resin composition according to an embodiment of the present invention may be, for example, 50% by weight to 100% by weight, 60% by weight to 100% by weight, 70% by weight to 100% by weight, 80% by weight to 100% by weight, 90% by weight to 100% by weight, 95% by weight to 100% by weight, or 98% by weight to 100% by weight.

[0076] As the inorganic substance, any appropriate inorganic substance can be adopted as long as it does not impair the effects of the present invention. Only one type of inorganic substance may be used, or two or more types may be used. Examples of such inorganic substances include gypsum, calcium carbonate, diatomaceous earth, calcium silicate, aluminum silicate, magnesium silicate, potassium titanate, silicon carbide, carbon fiber, glass fiber, metal fiber, dolomite, kaolin, talc, clay, silica, alumina, titanium oxide, aluminum hydroxide, magnesium hydroxide, magnesium oxide, mica, carbon black, and metal powder. Gypsum is preferred because it can further exhibit the effects of the present invention.

[0077] The content of the inorganic substance in the thermoplastic resin composition according to an embodiment of the present invention may be any appropriate content ratio as long as the effects of the present invention are not impaired. In terms of being able to further exhibit the effects of the present invention, the content of the inorganic substance in the thermoplastic resin composition according to an embodiment of the present invention is, for example, 10% by weight to 90% by weight, alternatively, 20% by weight to 80% by weight, 25% by weight to 70% by weight, 30% by weight to 65% by weight, 35% by weight to 60% by weight, or 40% by weight to 55% by weight.

[0078] The content of the inorganic substance in the thermoplastic resin composition according to an embodiment of the present invention is, for example, 10 parts by weight to 300 parts by weight, alternatively 30 parts by weight to 200 parts by weight, 50 parts by weight to 150 parts by weight, 70 parts by weight to 130 parts by weight, or alternatively 80 parts by weight to 120 parts by weight, in terms of being able to further exhibit the effects of the present invention, assuming that the content of the thermoplastic resin in the thermoplastic resin composition according to an embodiment of the present invention is 100 parts by weight.

[0079] <1-4. Other Components> The thermoplastic resin composition according to an embodiment of the present invention may contain other components in addition to the thermoplastic resin, inorganic substance, and impact modifier. The other components may be one type only, or two or more types. Any appropriate other components may be used as such other components as long as they do not impair the effects of the present invention. Examples of such other components include heat stabilizers, UV stabilizers, lubricants, rheology modifiers, antioxidants (phenolic, sulfur-based, phosphorus-based, etc.), slip agents, antistatic agents, dispersants, copper inhibitors, neutralizing agents, plasticizers, flame retardants, crosslinking agents, crosslinking aids, flow improvers such as peroxides, electrical property improvers, UV absorbers, light stabilizers, weld strength improvers, nucleating agents, antifogging agents, antiblocking agents, slip agents, colorants, metal deactivators, molecular weight modifiers, antibacterial agents, antifungal agents, fluorescent brighteners, weathering stabilizers, surfactants, compatibilizers, deodorizers, and insect repellents.

[0080] The content ratio of other components in the thermoplastic resin composition according to an embodiment of the present invention is, for example, 50% by weight or less, may be 0% by weight to 40% by weight, may be 0% by weight to 30% by weight, may be 0% by weight to 20% by weight, may be 0% by weight to 10% by weight, may be 0% by weight to 5% by weight, or may be 0% by weight to 2% by weight, in order to further exhibit the effects of the present invention.

[0081] 2. Uses of Thermoplastic Resin Composition The thermoplastic resin composition according to an embodiment of the present invention can be used in a variety of applications. Examples of such applications include materials made of plastic or wood, such as outdoor building materials such as wood decks, benches, walkways, fences, louvers, decking boards, pallets, flooring, stair treads, handrails, furniture, wall materials, interior materials, cutlery, tableware, trays, boat oars, archery bows, skis, keyboards, knife handles, sleepers, equipment housings, and consumable housings.

[0082] The present invention will be specifically described below using examples, but the present invention is not limited to these examples. The test and evaluation methods used in the examples are as follows. The term "parts" means "parts by weight" unless otherwise specified, and the term "%" means "% by weight" unless otherwise specified.

[0083] <Measurement of Charpy impact strength after extrusion molding> Using the obtained thermoplastic resin composition, a material was molded in an extrusion molding machine, and the material was cut into a flat plate. The flat plate was processed to prepare a test piece (notched) for measuring Charpy impact strength in accordance with JIS K 7111-1, and a Charpy impact test was performed in accordance with JIS K 7111-1.

[0084] <Measurement of Injection Molding Charpy Impact Strength> Using the obtained thermoplastic resin composition, a test piece (with a notch) for measuring Charpy impact strength was prepared in accordance with JIS K 7111-1 using an injection molding machine, and a Charpy impact test was performed in accordance with JIS K 7111-1.

[0085] [Production Example 1] A rubber component-containing foam material (1) was produced as follows with the formulation shown in Table 1. The rubber components included 50 parts by weight of ethylene-propylene-diene rubber (trade name "EPT3045", manufactured by Mitsui Chemicals, Inc., diene content 4.7% by weight), 50 parts by weight of ethylene-propylene-diene rubber (trade name "EP-24", manufactured by JSR Corporation, diene content 4.5% by weight), 5 parts by weight of zinc oxide (trade name "Zinc Oxide Type 2", manufactured by Mitsui Mining & Smelting Co., Ltd.) as a vulcanization aid, 3 parts by weight of stearic acid (trade name "Sakura Powdered Stearic Acid", manufactured by NOF Corporation) as a lubricant, and 100 parts by weight of calcium carbonate (trade name "N Heavy Calcium Carbonate", manufactured by Maruo Calcium Co., Ltd.) as a filler. , 10 parts by weight of carbon black (trade name "Asahi #50" manufactured by Asahi Carbon Co., Ltd.) as a pigment, 5 parts by weight of paraffin (trade name "Parapele 130" manufactured by Taniguchi Oil Co., Ltd., melting point: 54.4 to 57.2 ° C., needle penetration: 50 or less) as a softener, 130 parts by weight of asphalt (trade name "Blown Asphalt 10-20" manufactured by Nippon Oil Corporation, softening point: 135 to 142 ° C., needle penetration (25 ° C.): 10 to 20), 130 parts by weight of paraffin-based oil (paraffin-based process oil, trade name "Diana Process Oil PW-90" manufactured by Idemitsu Kosan Co., Ltd., density: 0.85 to 0.89 g / cm 340 parts by weight of a polyurethane foam, kinematic viscosity (40°C): 75.0 to 105.0 cSt, and 1 part by weight of a thiourea-based vulcanization accelerator (N,N'-dibutylthiourea, trade name "Noccela BUR", manufactured by Ouchi Shinko Chemical Co., Ltd.) were blended as a vulcanization accelerator, and the mixture was kneaded in a 3 L pressure kneader to prepare a primary mixture. Separately, the following were compounded: sulfur (trade name "Alphagran S-50EN", manufactured by Tochi Co., Ltd.) as a vulcanizing agent: 1.6 parts by weight; a thiazole-based vulcanization accelerator (2-mercaptobenzothiazole, trade name "Noccela M", manufactured by Ouchi Shinko Chemical Co., Ltd.) as a vulcanization accelerator: 0.45 parts by weight; a dithiocarbamic acid-based vulcanization accelerator (zinc dibenzyldithiocarbamate, trade name "Noccela ZTC", manufactured by Ouchi Shinko Chemical Co., Ltd.) as a vulcanization accelerator: 0.2 parts by weight; a thiuram-based vulcanization accelerator (tetrabenzyl thiuram disulfide, trade name "Noccela TBzTD", manufactured by Ouchi Shinko Chemical Co., Ltd.) as a foaming agent: 20 parts by weight; and a urea-based foaming accelerator (trade name "Cellpaste K5", manufactured by Eiwa Chemical Industry Co., Ltd.) as a foaming aid: 6.5 parts by weight. The resulting compound was then blended with the primary blend and kneaded using a 10-inch mixing roll to prepare a foam composition (secondary blend). The resulting foam composition was then extruded into a sheet approximately 8 mm thick using a single-screw extruder (45 mmφ) to produce a foam composition sheet. The resulting foam composition sheet was preheated at 120°C for 20 minutes in a hot air circulating oven. The oven was then heated to 160°C over 10 minutes, and then heated at 160°C for 20 minutes to vulcanize and foam, yielding a rubber component-containing foam material (1) containing a vulcanizate of ethylene-propylene-diene rubber. The volume expansion ratio (ratio of density before and after foaming) of the rubber component-containing foam material (1) was 13 times, and the apparent density (apparent density according to JIS K 6767) was 0.082 g / cm. 3 The average cell diameter was 468 μm.

[0086]

[0087] [Production Example 2] A rubber compound material (1) (non-foamed material) containing a vulcanizate of ethylene-propylene-diene rubber was obtained in the same manner as in Production Example 1, except that no vulcanization accelerator, foaming aid, or crosslinking agent was used.

[0088] Example 1 50 parts by weight of polypropylene (trade name "Recycled Talc-containing PP" manufactured by Washimi Kako Co., Ltd.), 50 parts by weight of gypsum (trade name "Pulverized Waste Gypsum Board 3 mm Under" manufactured by Chuo Environmental Development Co., Ltd.), and 10 parts by weight of the pulverized product of the rubber component-containing foamed material (1) obtained in Production Example 1 (pulverization conditions: pulverized with a BO4B-3072 ZFS manufactured by Horai Co., Ltd., mesh size 10 mm) were mixed using a Henschel mixer to obtain a thermoplastic resin composition (1). The results are shown in Table 2.

[0089] Example 2 A thermoplastic resin composition (2) was obtained in the same manner as in Example 1, except that 10 parts by weight of a pulverized waste material of an EPDM foam sealing material (trade name "EPTSealer (registered trademark) EE1000", manufactured by Nitto Denko Corporation) (pulverization conditions: pulverized with a BO4B-3072 ZFS manufactured by Horai Corporation, using a mesh size of 10 mm) was used instead of the pulverized material of the rubber component-containing foam material (1) obtained in Production Example 1. The results are shown in Table 2.

[0090] A thermoplastic resin composition (C1) was obtained in the same manner as in Example 1, except that 10 parts by weight of the pulverized rubber component-containing foamed material (1) obtained in Production Example 1 was not used. The results are shown in Table 2.

[0091] A thermoplastic resin composition (C2) was obtained in the same manner as in Example 1, except that 10 parts by weight of the rubber compounding material (1) obtained in Production Example 2 was used instead of 10 parts by weight of the pulverized rubber component-containing foamed material (1) obtained in Production Example 1. The results are shown in Table 2.

[0092] [Reference Example 1] A thermoplastic resin composition (R1) was obtained in the same manner as in Example 1, except that 10 parts by weight of ethylene-propylene-diene rubber (EPDM) (trade name "EPT3045", manufactured by Mitsui Chemicals) was used instead of 10 parts by weight of the pulverized rubber component-containing foam material (1) obtained in Production Example 1. The results are shown in Table 2.

[0093]

[0094] As shown in Table 2, the Charpy impact strength of the extrusion molding of the thermoplastic resin composition (R1) (Reference Example 1) produced using ethylene-propylene-diene rubber, a conventional non-foaming rubber component, as an impact modifier was 5.4 kJ / m 2 In comparison, the Charpy impact strength of the extrusion molding of the thermoplastic resin composition (C2) (Comparative Example 2) produced using a non-foamed impact modifier (containing a filler and a softener) was 4.4 kJ / m 2 It was found that the impact resistance was significantly reduced.

[0095] As shown in Table 2, the Charpy impact strength of the thermoplastic resin composition (1) (Example 1) produced using the rubber component-containing foam material (1) (containing a filler and a softener) as an impact modifier was 8.9 kJ / m. 2 The Charpy impact strength of the extrusion molding of the thermoplastic resin composition (2) (Example 2) produced using a waste EPDM foam sealing material as an impact modifier was 8.8 kJ / m 2 Thus, Examples 1 and 2 were found to have a Charpy impact strength (5.5 kJ / m) of extrusion molding of Comparative Example 1, which did not contain an impact resistance modifier. 2 ) was found to be significantly improved compared to Comparative Example 2. Furthermore, although Examples 1 and 2 contain additives like Comparative Example 2, the extrusion molding Charpy impact strength was found to be significantly improved compared to Comparative Example 2. Furthermore, Examples 1 and 2 were found to be significantly improved in extrusion molding Charpy impact strength compared to the thermoplastic resin composition (R1) (Reference Example 1) produced using ethylene-propylene-diene rubber, which is a conventional non-foamed rubber component.

[0096] Furthermore, as shown in Table 2, the injection molding Charpy impact strength of the thermoplastic resin composition (1) (Example 1) produced using the rubber component-containing foam material (1) (containing a filler and a softener) as an impact modifier was 6.5 kJ / m 2 The Charpy impact strength of the thermoplastic resin composition (2) (Example 2) produced using a waste EPDM foam sealant foam as an impact modifier was 6.1 kJ / m. 2Thus, Examples 1 and 2 had a Charpy impact strength (2.1 kJ / m) of injection molding of Comparative Example 1, which did not contain an impact modifier. 2 Furthermore, it was found that the injection molding Charpy impact strength of Examples 1 and 2 was significantly improved compared to Comparative Example 2, although both contained additives like Comparative Example 2.

[0097] The thermoplastic resin composition according to an embodiment of the present invention can be used for various materials that can be produced by, for example, extrusion molding or injection molding, and specifically can be used for materials made of plastic or wood, such as outdoor building materials such as wood decks, benches, walkways, fences, louvers, decking boards, pallets, flooring, stair treads, handrails, furniture, wall materials, interior materials, cutlery, tableware, trays, boat oars, archery bows, skis, keyboards, knife handles, sleepers, equipment housings, and consumable housings.

Claims

1. A thermoplastic resin composition comprising a thermoplastic resin and an impact modifier, wherein the impact modifier comprises a rubber-containing foam material.

2. The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin is at least one selected from the group consisting of polyolefin-based resins and polystyrene-based resins.

3. The thermoplastic resin composition according to claim 1, wherein said rubber-containing foam material comprises a vulcanizate of ethylene propylene diene rubber.

4. The thermoplastic resin composition according to claim 1, wherein the rubber-containing foam material is a waste material.

5. The thermoplastic resin composition according to claim 1, which contains an inorganic substance.

6. The thermoplastic resin composition according to any one of claims 1 to 5, which is used as an outdoor building material.

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