JP7499398B1 - Resin composition and molded article containing same - Google Patents

Abstract

[Problem] To provide a resin composition that has high elongation and tensile strength and is excellent in processability, despite containing inorganic powders containing manganese and iron. [Solution] The resin composition that solves the above problem contains a thermoplastic resin containing a polyolefin resin, an inorganic powder, and a metal deactivator, the content of the inorganic powder being 50% by mass or more and 90% by mass or less, the amount of manganese element in the inorganic powder being 0.001% by mass or more and 0.500% by mass or less, the amount of iron element in the inorganic powder being 0.01% by mass or more and 1.00% by mass or less, and the content of the metal deactivator being 0.2% by mass or more and 1.0% by mass or less. [Selected Figure] None

Description

The present invention relates to a resin composition and a molded article containing the same.

Conventionally, resin compositions have been known in which inorganic powders such as calcium carbonate powder are highly filled into thermoplastic resins (for example, Patent Document 1). Such resin compositions have the advantages of small thermal shrinkage and excellent impact resistance. In recent years, there have been studies on utilizing the properties of these resin compositions to expand their applications even further.

JP 2023-77472 A

In general, when processing a resin composition, stretching and various molding processes are performed according to the application. Therefore, excellent processability is required for the resin composition. In recent years, in order to protect the environment, calcium-containing waste such as steel slag and carbide slag, or calcium extracted from the waste, is reacted with carbon dioxide, which causes the greenhouse effect, to prepare inorganic powder (calcium carbonate). The inventors have conducted research and found that when inorganic powder made from such slag, especially inorganic powder containing iron and manganese, is used in the above resin composition, the processability of the resulting resin composition, especially the elongation and tensile strength, tends to be low.

The present invention has been made in consideration of the problems of the conventional technology described above. Specifically, the object of the present invention is to provide a resin composition that has high elongation and tensile strength and is excellent in processability, even though it contains inorganic powders that include manganese and iron, and to provide a molded article containing the same.

The inventors discovered that by combining a thermoplastic resin with an inorganic powder containing a certain amount of manganese and iron elements and a metal deactivator, the elongation and tensile strength of the resin composition are significantly improved, and its processability is also improved, leading to the completion of the present invention.

One aspect of the present invention provides the following resin composition.
[1] A resin composition comprising a thermoplastic resin containing a polyolefin resin, an inorganic powder, and a metal deactivator, wherein the content of the inorganic powder is 50% by mass or more and 90% by mass or less, the amount of manganese element in the inorganic powder is 0.001% by mass or more and 0.500% by mass or less, and the amount of iron element in the inorganic powder is 0.01% by mass or more and 1.00% by mass or less, and the content of the metal deactivator is 0.2% by mass or more and 1.0% by mass or less.
[2] The resin composition according to [1], wherein the thermoplastic resin comprises a polypropylene-based resin and/or a polyethylene-based resin.
[3] The resin composition according to [1] or [2], wherein the inorganic powder is calcium carbonate powder.
[4] The resin composition according to [3], wherein the calcium carbonate powder is calcium carbonate powder made from iron and steel slag and/or carbide slag.
[5] The resin composition according to [3] or [4], wherein the calcium carbonate powder has an average particle size of 0.7 μm or more and 10.0 μm or less, as measured by an air permeability method in accordance with JIS M-8511.
[6] The metal deactivator is selected from the group consisting of melamine, 3-salicylamino-1,2,4-triazole, N'1,N'12-bis(2-hydroxybenzoyl)dodecane dihydrazide, 1,2-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propanoyl]hydrazine, N,N'-diphenyloxamide, N-salicyl-N'-salicylhydrazine, N,N'-bis(salicyl)hydrazine, N,N'-bis(3,5-di-tert-butyl-4- The resin composition according to any one of [1] to [5], which contains one or more compounds selected from the group consisting of bis(phenyl)hydrazine, bis(benzylidene)oxalyl dihydrazide, oxanilide, isophthaloyl dihydrazide, sebacoyl bisphenylhydrazide, N,N'-diacetyladipoyl dihydrazide, N,N'-bis(salicyloyl)oxylyl dihydrazide, and N,N'-bis(salicyloyl)thiopropionyl dihydrazide.
[7] The resin composition according to [6], wherein the metal deactivator comprises one or more compounds selected from the group consisting of melamine, 3-salicylamino-1,2,4-triazole, N'1,N'12-bis(2-hydroxybenzoyl)dodecane dihydrazide, and 1,2-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propanoyl]hydrazine.
[8] The resin composition according to [7], wherein the metal deactivator is melamine.

One aspect of the present invention provides the following molded article.
[9] A molded article comprising the resin composition according to any one of [1] to [8] above.

The present invention provides a resin composition that has high elongation and tensile strength and is excellent in processability, despite containing inorganic powders including manganese and iron, and a molded article containing the same.

One embodiment of the present invention is described in detail below. However, the present invention is not limited to this embodiment. In addition, in this specification, a numerical range expressed using "~" means a range that includes the numerical values written before and after "~" as the lower and upper limits.

1. Resin composition The resin composition of this embodiment contains a thermoplastic resin containing a polyolefin resin, an inorganic powder, and a metal deactivator. The amount of manganese element in the inorganic powder is 0.001% by mass or more and 0.500% by mass or less, and the amount of iron element is 0.01% by mass or more and 1.00% by mass or less. As described above, when the inorganic powder contains manganese element or iron element, there is a problem that the processability of the resin composition is likely to be low. On the other hand, when the resin composition contains a certain amount of metal deactivator together with the inorganic powder and the thermoplastic resin, the elongation and tensile strength of the resin composition become significantly better, and the processability becomes very good, as demonstrated in the examples described later. Hereinafter, each component in the resin composition and the manufacturing method of the resin composition will be described.

(Thermoplastic resin)
The thermoplastic resin may contain only polyolefin-based resin, or may contain polyolefin-based resin and other resins. However, the thermoplastic resin preferably contains polyolefin-based resin as a main component. More specifically, the amount of polyolefin-based resin in the thermoplastic resin is preferably 80% by mass or more, more preferably 90% by mass or more, and even more preferably 95% by mass or more. The thermoplastic resin may contain only one type of polyolefin-based resin, or may contain two or more types of polyolefin-based resin.

A polyolefin resin is a resin whose main component is an olefin-derived structural unit, and the amount of the olefin-derived structural unit relative to all structural units constituting the polyolefin resin is 50% by mass or more. The polyolefin resin may be a homopolymer of one type of olefin, a copolymer of two or more types of olefins, or a copolymer of one or more types of olefins and one or more other monomers (monomers other than olefins). The amount of the olefin-derived structural unit in the polyolefin resin is preferably 75% by mass or more, more preferably 85% by mass or more, and even more preferably 90% by mass or more.

Examples of the olefins include ethylene and α-olefins having 3 to 10 carbon atoms, and specific examples thereof include ethylene, propylene, 1-butene, isobutylene, 1-pentene, 3-methyl-1-butene, 1-hexene, 3,4-dimethyl-1-butene, 1-heptene, 4-methylpentene-1, 3-methyl-1-hexene, and 1-octene. Polyolefin resins may contain only one type of structural unit derived from these, or may contain two or more types.

The other monomers are not particularly limited as long as they do not impair the purpose and effect of this embodiment. Examples of other monomers include diene monomers such as 1,4-hexadiene, 1,6-octadiene, 5-methyl-1,4-hexadiene, 3,7-dimethyl-1,6-octadiene, dicyclopentadiene (DCPD), ethylidenenorbornene (ENB), norbornadiene, and 5-vinyl-2-norbornene; acid (or acid anhydride) modified olefins such as maleic anhydride modified olefins; (meth)acrylates such as methyl (meth)acrylate; and the like. The polyolefin resin may contain only one type of structural unit derived from these, or may contain two or more types.

The polyolefin resin is preferably a polypropylene resin and/or a polyethylene resin. The polypropylene resin and the polyethylene resin may be virgin resin, recycled resin, or a mixture of these.

In this specification, the term "polypropylene-based resin" refers to a resin containing 50% or more by mass of structural units derived from propylene, and refers to a propylene homopolymer or a copolymer of propylene and other monomers (propylene copolymer). Propylene homopolymers include isotactic, syndiotactic, atactic, hemiisotactic, and linear or branched polypropylenes exhibiting various stereoregularities. The stereoregularity of propylene can be determined by ¹³ C-NMR or the like. The propylene copolymer may be a random copolymer or a block copolymer. The propylene copolymer may be a binary copolymer of propylene and other monomers, or a multicomponent copolymer of propylene and two or more other monomers. Examples of preferred copolymerization components (other monomers) include ethylene, α-olefins having 4 or more carbon atoms, tetrafluoroethylene, vinyl acetate, and the like. In this embodiment, the polypropylene-based resin is preferably a propylene homopolymer or a propylene copolymer containing less than 5% by mass of structural units derived from other monomers.

On the other hand, in this specification, the term "polyethylene resin" refers to a resin containing 50% or more by mass of structural units derived from ethylene, and refers to an ethylene homopolymer or a copolymer of ethylene and other monomers (ethylene copolymer). Examples of ethylene homopolymers include high density polyethylene (HDPE), low density polyethylene (LDPE), medium density polyethylene, linear low density polyethylene (LLDPE), etc. In addition, the ethylene copolymer may be a binary copolymer of ethylene and other monomers, or a multi-component copolymer of ethylene and two or more other monomers. Examples of preferred copolymerization components (other monomers) include vinyl acetate and α-olefins having 3 or more carbon atoms. In this embodiment, the polyethylene resin is preferably an ethylene homopolymer or an ethylene copolymer containing less than 5% by mass of structural units derived from other monomers.

The thermoplastic resin may further contain a resin other than the polyolefin-based resin, as described above. Examples of resins other than the polyolefin-based resin include thermoplastic resins such as poly(meth)acrylic acid (ester), polyvinyl acetate, polyacrylonitrile, polystyrene, ABS resin, polycarbonate, polyamide, polyvinyl alcohol, petroleum hydrocarbon resin, and coumarone-indene resin; and elastomers such as styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-butadiene-ethylene copolymer, styrene-isoprene-ethylene copolymer, acrylonitrile-butadiene copolymer, and fluorine-based elastomer.

The content of the thermoplastic resin in the resin composition is preferably 10% by mass or more and 49.8% by mass or less, more preferably 15% by mass or more and 45% by mass or less, and even more preferably 18% by mass or more and 43% by mass or less. The content mass ratio of the amount of the thermoplastic resin to the inorganic powder described below is preferably in the range of 50:50 to 10:90, and more preferably 45:55 to 15:85. When the amount of the thermoplastic resin is in this range, not only is the amount of thermal shrinkage of the resin composition small and the impact resistance good, but the processability is also likely to be further improved.

(Inorganic powder)
The inorganic powder is a powder made of an inorganic substance, and the amount of manganese element is 0.001 mass% or more and 0.500 mass% or less, and the amount of iron element is 0.01 mass% or more and 1.00 mass% or less. The amount of manganese element and the amount of iron element in the inorganic powder can be determined by an ICP emission spectrometer or the like. The manganese and iron may be contained in the inorganic powder as simple substances, or may be contained as compounds with other elements such as oxides, sulfides, nitrides, and sulfides.

The type of inorganic substance is selected according to the application of the resin composition. Examples of the inorganic substance include carbonates, sulfates, silicates, phosphates, borates, oxides, or hydrates of calcium, magnesium, aluminum, titanium, zinc, silicon, barium, molybdenum, sodium, and potassium. Examples of the inorganic substance also include inorganic carbon compounds. Specific examples of the inorganic substance include calcium carbonate, magnesium carbonate, zinc oxide, titanium oxide, silica, alumina, clay (e.g., talc, kaolin, etc.), aluminum hydroxide, magnesium hydroxide, aluminum silicate, magnesium silicate, calcium silicate, aluminum sulfate, magnesium sulfate, calcium sulfate, magnesium phosphate, barium sulfate, silica sand, carbon black, zeolite, molybdenum, diatomaceous earth, sericite, shirasu, calcium sulfite, sodium sulfate, potassium titanate, bentonite, wollastonite, dolomite, graphite, etc. These may be synthetic or made from natural minerals. The inorganic powder may contain only one of these, or two or more of them.

The shape of the inorganic powder is not particularly limited, and may be any of particles, flakes, granules, fibers, etc. In the case of particles, the powder may be spherical, as is generally obtained by synthetic methods, or irregularly shaped, as is obtained by crushing collected natural minerals.

Preferred examples of inorganic powders include calcium carbonate, magnesium carbonate, dolomite, zinc oxide, titanium oxide, silica, alumina, clay, talc, kaolin, aluminum hydroxide, and magnesium hydroxide powders, and calcium carbonate powder is particularly preferred. Calcium carbonate may be prepared by a synthetic method, that is, light calcium carbonate. On the other hand, it may be heavy calcium carbonate, which is obtained by mechanically crushing and classifying natural raw materials mainly composed of _CaCO3 such as limestone. Furthermore, it may be a combination of light calcium carbonate and heavy calcium carbonate.

In this embodiment, the calcium carbonate powder is preferably a powder made from concrete sludge, steel slag, carbide slag, waste concrete, coal ash, biomass ash, incineration ash, waste gypsum, alkaline wastewater, etc., and more preferably a powder made from steel slag and/or carbide slag. Calcium carbonate powders made from these raw materials often contain the above-mentioned amounts of manganese and iron elements.

上記式における（^１３Ｃ／^１２Ｃ）_基準は、０．０１１であり、（^１３Ｃ／^１２Ｃ）_試料は、炭酸カルシウム粉末中の^１２Ｃの量に対する、^１３Ｃの量である。これらは、公知の方法で測定可能である。 Moreover, from the viewpoint of environmental consideration, it is more preferable that the calcium carbonate powder contains carbon derived from fossil fuels (industrial exhaust gas). Whether or not the calcium carbonate powder contains carbon derived from fossil fuels can be easily determined by identifying the carbon isotopes. Specifically, it can be identified by the deviation of the carbon isotope of the calcium carbonate powder from a reference value represented by the following formula (hereinafter also referred to as "δ ¹³ C value").

In the above formula, the ( ¹³ C/ ¹² C) _standard is 0.011, and the ( ¹³ C/ ¹² C) _sample is the amount of ¹³ C relative to the amount of ¹² C in the calcium carbonate powder. These can be measured by known methods.

Generally, the δ ¹³ C value of coal is −30% to −20%, and methane is −20% or less. On the other hand, the δ ¹³ C value of carbon dioxide in the atmosphere is about −10% to −7%. Therefore, when the δ ¹³ C value is less than −10%, it can be said that the calcium carbonate powder contains carbon derived from fossil fuels (industrial exhaust gas), and the δ ¹³ C value of the calcium carbonate powder is preferably less than −10%.

Here, the inorganic powder may be surface-modified or may not be surface-modified. From the viewpoint of dispersibility of the inorganic powder, it is preferable that the inorganic powder is surface-modified. Examples of surface modification methods of inorganic powder include physical modification methods using plasma treatment, etc., and chemical modification methods using coupling agents, surfactants, etc. Examples of coupling agents that can be used in chemical modification methods include silane coupling agents and titanium coupling agents. As surfactants, any of anionic, cationic, nonionic, and amphoteric surfactants can be used, and examples thereof include higher fatty acids, higher fatty acid esters, higher fatty acid amides, and higher fatty acid salts.

The average particle size of the inorganic powder is not particularly limited and is appropriately selected depending on the shape and thickness of the molded product, but is preferably 0.7 μm to 10.0 μm, more preferably 0.7 μm to 6.0 μm, and even more preferably 1.0 μm to 4.0 μm. The average particle size of the inorganic powder in this specification refers to a value calculated from the measurement results of the specific surface area by the air permeation method according to JIS M-8511. An example of a measuring instrument is the specific surface area measuring device SS-100 type manufactured by Shimadzu Corporation. If the average particle size of the inorganic powder is 10.0 μm or less, the inorganic powder is less likely to fall off from the molded product obtained from the resin composition. It is preferable that the inorganic powder does not contain particles with a particle size of 45 μm or more in its particle size distribution. On the other hand, if the average particle size is 0.7 μm or more, the viscosity when kneaded with the thermoplastic resin is likely to fall within the desired range.

The amount of inorganic powder in the resin composition of this embodiment may be 50% by mass or more and 90% by mass or less, more preferably 55 parts by mass or more and 85 parts by mass or less, and even more preferably 57 parts by mass or more and 82 parts by mass or less, relative to the total amount of the resin composition. As described above, the content mass ratio of the thermoplastic resin and the inorganic powder is preferably in the range of 50:50 to 10:90. When the amount of inorganic powder is in this range, not only is the amount of thermal shrinkage of the resin composition small and the impact resistance good, but the processability is also likely to be further improved.

(Metal deactivator)
The metal deactivator may be any compound capable of interacting with the manganese and iron elements contained in the inorganic powder and deactivating them. Specific examples of the metal deactivator include melamine, 3-salicylamino-1,2,4-triazole, N'1,N'12-bis(2-hydroxybenzoyl)dodecane dihydrazide, 1,2-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propanoyl]hydrazine, N,N'-diphenyloxamide, N-salicyl-N'-salicylhydrazine, N,N'-bis(salicyl)hydrazine, N,N'-biphenyloxamide, N-salicyl-N'-salicylhydrazine, N,N'-bis(salicyl)hydrazine, N,N'-biphenyloxamide, N-salicyl-N'-salicylhydrazine, N,N'-bis(salicyl)hydrazine, N,N'-biphenyloxamide, N-salicyl-N'-salicylhydrazine, N,N'-bis(salicyl)hydrazine, N,N'-biphenyloxamide, N-salicyl-N'-salicylhydrazine, N,N'-biphenyloxamide, N-salicyl- ... Examples of the metal deactivators include bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazine, bis(benzylidene)oxalyl dihydrazide, oxanilide, isophthaloyl dihydrazide, sebacoyl bisphenylhydrazide, N,N'-diacetyladipoyl dihydrazide, N,N'-bis(salicyloyl)oxylyl dihydrazide, and N,N'-bis(salicyloyl)thiopropionyl dihydrazide. The resin composition may contain only one type of metal deactivator, or may contain two or more types.

Among the above, melamine, 3-salicylamino-1,2,4-triazole, N'1,N'12-bis(2-hydroxybenzoyl)dodecane dihydrazide, and 1,2-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propanoyl]hydrazine are preferred, with melamine being particularly preferred. When the metal deactivator is melamine, the elongation and tensile strength of the resin composition tend to be significantly increased, as shown in the examples below. This is thought to be because melamine not only deactivates the manganese and iron elements in the inorganic powder, but also because melamine (metal deactivator) interacts with the thermoplastic resin and inorganic powder.

The amount of metal deactivator in the resin composition of this embodiment may be 0.2 mass% or more and 1.0 mass% or less, more preferably 0.2 mass% or more and 0.8 mass% or less, and more preferably 0.3 mass% or more and 0.6 mass% or less, relative to the total amount of the resin composition. When the amount of metal deactivator is 0.2 mass% or more, the effect of adding the metal deactivator is easily obtained. On the other hand, if the amount of metal deactivator is excessively large, the elongation and tensile strength of the resin composition tend to decrease, but when the amount is 1.0 mass% or less, good elongation and tensile strength are easily obtained.

(Other ingredients)
The resin composition may further contain components other than those described above, provided that the purpose and effect of the present embodiment are not impaired. Examples of the components other than those described above include lubricants, plasticizers, colorants, antioxidants, flame retardants, foaming agents, flow control agents, etc.

Examples of lubricants include fatty acid-based lubricants such as stearic acid, hydroxystearic acid, complex stearic acid, and oleic acid; fatty alcohol-based lubricants; fatty amide-based lubricants such as stearamide, oxystearamide, oleylamide, erucylamide, ricinoleamide, behenamide, methylolamide, methylene bisstearamide, methylene bisstearbehenamide, bisamic acids of higher fatty acids, and complex amides; fatty ester-based lubricants such as n-butyl stearate, methyl hydroxystearate, polyhydric alcohol fatty acid esters, saturated fatty acid esters, and ester waxes; and fatty acid metal soap-based lubricants such as zinc stearate and magnesium stearate.

Examples of plasticizers include, for example, triethyl citrate, acetyl triethyl citrate, dibutyl phthalate, diaryl phthalate, dimethyl phthalate, diethyl phthalate, dioctyl phthalate, di(2-ethylhexyl) phthalate, di-2-methoxyethyl phthalate, dibutyl tartrate, o-benzoyl benzoic acid ester, diacetin, epoxidized soybean oil, etc. The resin composition may contain these alone or in combination.

The coloring material may be any of the known organic or inorganic pigments or dyes. Specific examples of coloring materials include organic pigments such as azo-based, anthraquinone-based, phthalocyanine-based, quinacridone-based, isoindolinone-based, diosadin-based, perinone-based, quinophthalone-based, and perylene-based pigments; and inorganic pigments such as ultramarine, titanium yellow, and chromium oxide. The resin composition may contain one or more of these.

Examples of antioxidants include phosphorus-based antioxidants, phenol-based antioxidants, and pentaerythritol-based antioxidants. The resin composition may contain these antioxidants alone or in combination. Phosphorus-based, more specifically phosphorus-based antioxidant stabilizers such as phosphite esters and phosphate esters, are preferably used. Examples of phosphite esters include triesters, diesters, and monoesters of phosphorous acid, such as triphenyl phosphite, trisnonylphenyl phosphite, and tris(2,4-di-t-butylphenyl) phosphite.

Examples of phosphate esters include trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, triphenyl phosphate, tricresyl phosphate, tris(nonylphenyl)phosphate, 2-ethylphenyldiphenyl phosphate, etc.

Examples of phenolic antioxidants include α-tocopherol, butyl hydroxytoluene, sinapyl alcohol, vitamin E, n-octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 2-t-butyl-6-(3'-t-butyl-5'-methyl-2'-hydroxybenzyl)-4-methylphenylacrylate, 2,6-di-t-butyl-4-(N,N-dimethylaminomethyl)phenol, 3,5-di-t-butyl-4-hydroxybenzylphosphonate diethyl ester, and tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyloxymethyl]methane.

The flame retardant is not particularly limited, but may be, for example, a halogen-based flame retardant or a non-phosphorus-based halogen-based flame retardant such as a phosphorus-based flame retardant or a metal hydrate. The resin composition may contain one of these alone or two or more of them.

Examples of halogen-based flame retardants include halogenated bisphenol compounds such as halogenated bisphenylalkanes, halogenated bisphenylethers, halogenated bisphenylthioethers, and halogenated bisphenylsulfones, and bisphenol-bis(alkyl ether) compounds such as brominated bisphenol A, brominated bisphenol S, chlorinated bisphenol A, and chlorinated bisphenol S. Examples of phosphorus-based flame retardants include aluminum tris(diethylphosphinate), bisphenol A bis(diphenyl phosphate), triarylisopropyl phosphate, cresyl di-2,6-xylenyl phosphate, and aromatic condensed phosphate esters. Examples of metal hydrates include aluminum trihydrate, magnesium dihydroxide, or a combination thereof.

The flame retardant may also be combined with a flame retardant assistant. Examples of flame retardant assistants include antimony oxides such as antimony trioxide and antimony pentoxide, and other known flame retardant assistants.

There are no particular limitations on the foaming agent, so long as it is a compound capable of generating bubbles when mixed or pressed into a composition in a molten state in a melt kneader. Examples of foaming agents include those that change phase from solid to gas to generate bubbles, those that change phase from liquid to gas to generate bubbles, and gas itself.

Examples of blowing agents include aliphatic hydrocarbons such as propane, butane, pentane, hexane, and heptane; alicyclic hydrocarbons such as cyclobutane, cyclopentane, and cyclohexane; halogenated hydrocarbons such as chlorodifluoromethane, difluoromethane, trifluoromethane, trichlorofluoromethane, dichloromethane, dichlorofluoromethane, dichlorodifluoromethane, chloromethane, chloroethane, dichlorotrifluoroethane, dichloropentafluoroethane, tetrafluoroethane, difluoroethane, pentafluoroethane, trifluoroethane, dichlorotetrafluoroethane, trichlorotrifluoroethane, tetrachlorodifluoroethane, and perfluorocyclobutane; inorganic gases such as carbon dioxide, nitrogen, and air; and water.

The foaming agent may contain the active ingredient of the foaming agent together with the carrier resin. Examples of the carrier resin include crystalline olefin resins such as crystalline propylene. Examples of the active ingredient include bicarbonates. Of these, bicarbonates are preferred. A foaming agent concentrate containing crystalline polypropylene resin as the carrier resin and bicarbonates as the thermal decomposition type foaming agent is preferred.

As the flow control agent, known agents can be used. Examples of flow control agents include peroxides such as dialkyl peroxides, for example, 1,4-bis[(t-butylperoxy)isopropyl]benzene. Depending on the type of thermoplastic resin used, these peroxides can also act as crosslinking agents. In particular, when the thermoplastic resin (polyolefin resin) has a diene-derived structural unit, the diene can be crosslinked by the peroxide.

Examples of antistatic agents include fatty acid diethanolamides such as lauryl diethanolamide and stearyl diethanolamide; and hydroxyl group-containing compounds such as alcohol amine compounds. In particular, alcohol amines, such as monoethanolamine, diethanolamine, and triethanolamine, are preferred. Two or more types of antistatic agents can be used in combination. These antistatic agents may be supported on calcium silicate, calcium carbonate, or the like. The carbon number of the acyl group of the fatty acid diethanolamide is preferably in the range of 8 to 22 in terms of exerting a sufficient antistatic effect.

(Shape of resin composition)
The shape of the resin composition of the present embodiment is not particularly limited, and may be any shape such as a particulate shape, a pellet shape, or a lump shape. When the resin composition is in the form of a pellet, the shape of the pellet is not particularly limited, and may be any shape such as a cylindrical shape, a spherical shape, or an elliptical sphere. The size is also not particularly limited, and is appropriately selected according to the shape. For example, in the case of a spherical pellet, the diameter may be 1 to 10 mm. In the case of an elliptical sphere pellet, the major axis may be about 1 to 10 mm, and the aspect ratio may be about 0.1 to 1.0. In the case of a cylindrical pellet, the diameter may be about 1 to 10 mm, and the height may be about 1 to 10 mm.

(Method for producing resin composition)
The method for producing the resin composition is not particularly limited. The above-mentioned thermoplastic resin, inorganic powder, metal deactivator, and other components as necessary may be mixed sufficiently, and may be prepared, for example, by melt kneading. At this time, all components may be mixed and then melt kneaded, or only a portion of the components may be melt kneaded first, and the remaining components may be kneaded later. The device for melt kneading is not particularly limited, and a general extruder, kneader, Banbury mixer, etc. may be used. In particular, from the viewpoint of obtaining a resin composition with a uniform composition, it is preferable to knead with a twin-screw kneader.

2. Molded Article This embodiment also provides a molded article of the above-mentioned resin composition. The molding method of the above-mentioned resin composition is not particularly limited and is appropriately selected depending on the application. The above-mentioned resin composition has excellent processability and tensile strength, so that it can be molded into a desired shape by any method.

Examples of processing methods for the resin composition include inflation molding, extrusion molding, injection molding, foam injection molding, injection compression molding, blow molding, press molding, calendar molding, vacuum molding, etc. The shape and use of the molded product obtained from the resin composition are not particularly limited, and examples include films, sheets, containers (food containers, etc.), daily necessities, automotive parts, electrical and electronic parts, various consumables, etc.

The present invention will be described in detail with reference to examples, but the present invention is not limited to these examples.

[material]
The following components were used in each of the examples and comparative examples.

(Inorganic powder)
GCC (calcium bicarbonate powder (no surface treatment) manufactured by Bihoku Funka Kogyo Co., Ltd., average particle size: 2.2 μm, Mn content: <0.001% by mass, Fe content: 0.005% by mass)
CCU1 (calcium carbonate powder made from steel slag, average particle size: 3.5 μm, Mn content: 0.1% by mass, Fe content: 0.5% by mass)
CCU2 (calcium carbonate powder made from carbide slag, average particle size: 4.0 μm, Mn content: 0.005% by mass, Fe content: 0.1% by mass)

(Thermoplastic resin)
PP1 (homopolypropylene, Prime Polymer, E111G)
・PP2 (recycled polypropylene)

(Metal Deactivators)
CDA-1 (3-(N-salicyloyl)amino-1,2,4-triazole, manufactured by ADEKA Corporation, Adekastab CDA-1)
CDA-6S (N'1,N'12-bis(2-hydroxybenzoyl)dodecane dihydrazide, manufactured by ADEKA Corporation, Adekastab CDA-6S)
CDA-10 (N,N'-bis(salicyl)hydrazine, manufactured by ADEKA Corporation, Adekastab CDA-10)
・ZS-27 (melamine, manufactured by ADEKA, Adekastab ZS-27)
・ZS-90 (ADEKA Corporation, Adeka STAB ZS-90)
・ZS-91 (ADEKA Corporation, Adeka STAB ZS-91)
MD1024 (N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazine, manufactured by BASF, Irganox MD1024)

(others)
・Lubricant (stearic acid, Kao Corporation)
・Antistatic agent (lithium salt, manufactured by Marubishi Petrochemical Co., Ltd.)
Antioxidant 1 (phenolic antioxidant, manufactured by ADEKA Corporation)
Antioxidant 2 (phosphite-based antioxidant, manufactured by ADEKA Corporation)

[Production of resin compositions and molded articles of Reference Examples 1 and 2, Comparative Examples 1 and 2, and Examples 1 to 13]
Calcium carbonate powder, thermoplastic resin, metal deactivator, and other components were fed into a Parker HK-25D co-rotating twin screw kneading extruder (φ25 mm, L/D=41) in the composition ratios shown in Table 1, and strand extruded at a cylinder temperature of 230°C. The extruded ...

[Production of resin compositions and molded articles of Examples 14 to 19]
The pellets prepared in Examples 8 to 13 were used as masterbatches, and 80 parts by mass of these pellets and 20 parts by mass of a thermoplastic resin (PP1) were mixed and fed into a T-die extrusion molding device (φ20 mm, L/D=25) manufactured by Toyo Seiki Seisakusho, and extruded at 240°C to obtain a sheet. At this time, sheets were produced with a draw ratio of 1x (no draw), 2x, 3x, and 4x in the take-off direction. The draw conditions were a cast temperature of 70°C and a draw temperature of 100°C.

[evaluation]
For the sheets produced from each of the above-mentioned resin compositions, elongation, tensile properties, extensibility, and tensile properties of the stretched sheets were evaluated by the following methods.

Measurement of elongation and tensile strength From the sheets with a stretch ratio of 1 (without stretching) prepared in the above Examples, Comparative Examples, and Reference Examples, dumbbell-shaped test pieces were prepared in accordance with JIS K7161-2:2014. The elongation at break and tensile strength of the test pieces were measured using an autograph AG-100kNXplus (manufactured by Shimadzu Corporation) under conditions of 23°C and 50% RH in accordance with JIS K7161-2:2014. The test speed was 50 mm/min. The results are shown in Tables 1 and 2.

Stretchability Based on the appearance of the stretched sheets produced in the above Examples, Comparative Examples, and Reference Examples, the stretchability of each resin composition was evaluated according to the following criteria. Δ or higher is within the range where there is no problem in practical use. The results are shown in Tables 1 and 2.
◯: No stretching unevenness, and thickness and density variations are within 5%. Δ: No stretching unevenness, and thickness and density variations are within 10%. ×: There is stretching unevenness, or the film breaks during stretching, or the thickness and density variations exceed 10%.

Measurement of elongation and tensile strength of stretched sheets From the sheets stretched 3 times in the above examples, comparative examples, and reference examples, dumbbell-shaped test pieces were prepared in accordance with JIS K7161-2:2014. The elongation and tensile strength were measured in the same manner as above. The results are shown in Tables 1 and 2.

[Discussion]
As shown in Tables 1 and 2 above, when the inorganic powder contained manganese and iron elements but no metal deactivator (Comparative Examples 1 and 2), the elongation and tensile properties were lower in both cases compared to when the inorganic powder contained almost no manganese or iron elements (Reference Examples 1 and 2).

In contrast, by adding 0.01% by mass or more and 1.00% by mass or less of the metal deactivator to the total amount of the resin composition, the elongation and tensile properties of the resin composition were significantly improved (Examples 1 to 19). In particular, when ZS-27 (melamine) was added as a metal deactivator, the resin composition had even better processability than when the inorganic powder contained almost no manganese or iron elements (Reference Examples 1 and 2) (e.g., Examples 4, 10 to 13, and 16 to 19).

According to the resin composition of the present invention, a resin composition having high elongation and tensile strength and excellent processability can be obtained, even though it contains inorganic powder containing manganese and iron, and a molded product containing the same can be obtained. Therefore, it is possible to use inorganic powder made from steel slag, carbide slag, etc., and it is useful in the field of manufacturing various industrial products.

Claims (6)

A thermoplastic resin including a polyolefin resin;
Inorganic powder;
A metal deactivator;
Including,
The inorganic powder is calcium carbonate powder made from iron and steel slag and/or carbide slag,
The metal deactivator may be selected from the group consisting of melamine, 3-salicylamino-1,2,4-triazole, N'1,N'12-bis(2-hydroxybenzoyl)dodecane dihydrazide, 1,2-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propanoyl]hydrazine, N,N'-diphenyloxamide, N-salicyl-N'-salicylhydrazine, N,N'-bis(salicyl)hydrazine, N,N'-bis(3,5-di-t tert-butyl-4-hydroxyphenylpropionyl)hydrazine, bis(benzylidene)oxalyl dihydrazide, oxanilide, isophthaloyl dihydrazide, sebacoyl bisphenylhydrazide, N,N'-diacetyladipoyl dihydrazide, N,N'-bis(salicyloyl)oxylyl dihydrazide, and N,N'-bis(salicyloyl)thiopropionyl dihydrazide;
The content of the inorganic powder is 50% by mass or more and 90% by mass or less,
The amount of manganese element in the inorganic powder is 0.001% by mass or more and 0.500% by mass or less, and the amount of iron element in the inorganic powder is 0.01% by mass or more and 1.00% by mass or less,
The content of the metal deactivator is 0.2% by mass or more and 1.0% by mass or less;
Resin composition. The thermoplastic resin includes a polypropylene-based resin and/or a polyethylene-based resin.
The resin composition according to claim 1. The calcium carbonate powder has an average particle size of 0.7 μm or more and 10.0 μm or less, as measured by an air permeability method in accordance with JIS M-8511.
The resin composition according to claim 1 . the metal deactivator comprises one or more compounds selected from the group consisting of melamine, 3-salicylamino-1,2,4-triazole, N'1,N'12-bis(2-hydroxybenzoyl)dodecane dihydrazide, and 1,2-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propanoyl]hydrazine;
The resin composition according to claim 1 . The metal deactivator is melamine.
The resin composition according to claim 4 . The resin composition according to any one of claims 1 to 5 is included.
Molding.