WO2019159743A1 - 造核剤、これを用いたポリオレフィン系樹脂組成物およびその成形品 - Google Patents
造核剤、これを用いたポリオレフィン系樹脂組成物およびその成形品 Download PDFInfo
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- WO2019159743A1 WO2019159743A1 PCT/JP2019/003907 JP2019003907W WO2019159743A1 WO 2019159743 A1 WO2019159743 A1 WO 2019159743A1 JP 2019003907 W JP2019003907 W JP 2019003907W WO 2019159743 A1 WO2019159743 A1 WO 2019159743A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0083—Nucleating agents promoting the crystallisation of the polymer matrix
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
- C08K5/523—Esters of phosphoric acids, e.g. of H3PO4 with hydroxyaryl compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
- C07F9/6574—Esters of oxyacids of phosphorus
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
- C07F9/6574—Esters of oxyacids of phosphorus
- C07F9/65744—Esters of oxyacids of phosphorus condensed with carbocyclic or heterocyclic rings or ring systems
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/527—Cyclic esters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
- C08K5/5333—Esters of phosphonic acids
- C08K5/5357—Esters of phosphonic acids cyclic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/24—Crystallisation aids
Definitions
- the present invention relates to a nucleating agent, a polyolefin resin composition using the nucleating agent, and a molded article thereof, and more specifically, a nucleating agent capable of simultaneously improving the thermal stability and transparency of a polyolefin resin, and the same.
- the present invention relates to a polyolefin resin composition and a molded product thereof.
- Olefin resins such as polyethylene, polypropylene, and polybutene-1 have advantages such as excellent moldability, heat resistance, mechanical properties, and low specific gravity, and are widely used in films, sheets, and various molded products (structural parts, etc.). It's being used.
- olefin resins have problems such as a long molding cycle during processing because of a slow crystallization rate after thermoforming, and the molded product may be deformed due to crystallization that proceeds after molding. there were.
- the strength of the molded product is insufficient or large transparency is generated because large crystals are produced during the heat molding.
- defects are derived from the crystallinity of the olefin resin, and it is known that these defects can be solved by rapidly generating fine crystals.
- methods such as adding a nucleating agent or a crystallization accelerator are used.
- nucleating agents conventionally, sodium benzoate, 4-tert-butyl aluminum benzoate, sodium adipate, disodium bicyclo [2.2.1] heptane-2,3-dicarboxylate, etc.
- sodium-2,2′-methylenebis (4,6-di-tert-butylphenyl) phosphate significantly improves the rigidity, heat distortion temperature, and crystallization temperature of the polyolefin resin, and Excellent effects in improving heat resistance and transparency.
- sodium-2,2'-methylenebis (4,6-di-tert-butylphenyl) phosphate does not always improve the heat resistance and transparency of the polyolefin resin. That is, even with sodium-2,2′-methylenebis (4,6-di-tert-butylphenyl) phosphate, there are variations in the heat resistance and transparency improvement effect of the polyolefin resin, and these cannot be improved at the same time. The present situation is that improvement is desired.
- an object of the present invention is to provide a nucleating agent that can solve the above problems and can simultaneously improve the thermal stability and transparency of a polyolefin resin, a polyolefin resin composition using the nucleating agent, and a molded product thereof. There is.
- the present inventors have found that even a nucleating agent containing sodium-2,2′-methylenebis (4,6-di-tert-butylphenyl) phosphate, It has been found that the above problem occurs when the ratio of P / Na deviates from a specific range in relation to other components which are impurities. Based on such knowledge, the present inventors have conducted further intensive studies. As a result, the inventors have found that the above-described problems can be solved by adopting the following configuration, and have completed the present invention.
- the nucleating agent of the present invention has the following general formula (1), (In the general formula (1), R 1 to R 4 each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 9 carbon atoms, and R 5 represents a carbon atom.
- R 1 to R 4 each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 9 carbon atoms
- R 5 represents a carbon atom.
- M represents a hydrogen atom or a sodium atom
- the mass ratio P / Na of phosphorus atoms and sodium atoms in the nucleating agent is in the range of 1.200 to 1.500.
- the mass ratio P / Na of phosphorus atoms and sodium atoms in the nucleating agent is preferably in the range of 1.350 to 1.450.
- the polyolefin resin composition of the present invention is characterized in that 0.001 to 10 parts by mass of the nucleating agent of the present invention is contained with respect to 100 parts by mass of the polyolefin resin.
- the molded product of the present invention is characterized in that the polyolefin resin composition of the present invention is molded.
- nucleating agent capable of simultaneously improving the thermal stability and transparency of a polyolefin resin, a polyolefin resin composition using the same, and a molded product thereof.
- the nucleating agent of the present invention has the following general formula (1), It is a nucleating agent containing the compound represented by these.
- R 1 to R 4 each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 9 carbon atoms
- R 5 represents Represents an alkanediyl group having 1 to 4 carbon atoms
- M represents a hydrogen atom or a sodium atom.
- Examples of the alkyl group having 1 to 9 carbon atoms represented by R 1 , R 2 , R 3 and R 4 in the general formula (1) include, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, Butyl group, sec-butyl group, tert-butyl group, isobutyl group, amyl group, isoamyl group, tert-amyl group, hexyl group, cyclohexyl group, heptyl group, isoheptyl group, tert-heptyl group. Of these, those having a tert-butyl group are particularly preferred.
- alkanediyl group having 1 to 4 carbon atoms represented by R 5 in the general formula (1) examples include methylene, ethylene, propane-1,3-diyl, propane-1,2-diyl, butane- 1,4-diyl, butane-1,3-diyl and the like can be mentioned. Preferably, it is methylene.
- the mass ratio P / Na of phosphorus atoms and sodium atoms in the nucleating agent is in the range of 1.200 to 1.500.
- P / Na is less than 1.200, a large amount of sodium salt other than the compound represented by the general formula (1) is contained, and the nucleating agent becomes alkaline and becomes phenolic antioxidant. The composition and its cured product will turn yellow.
- P / Na exceeds 1.500, among the compounds represented by the general formula (1) in the nucleating agent, the proportion of the compound in which M is a hydrogen atom increases, and the transparency performance and It will not be possible to ensure sufficient thermal stability.
- P / Na is between 1.350 and 1.450.
- the method for producing the compound represented by the general formula (1) relating to the nucleating agent of the present invention is not particularly limited.
- phosphorus trichloride or phosphorus oxychloride
- 2,2′- After reacting with alkylidene bisphenol, it is hydrolyzed as necessary to form a cyclic acidic phosphate ester, then the obtained cyclic acidic phosphate ester is reacted with sodium hydroxide, and the resulting compound is filtered.
- M is a sodium atom
- the nucleating agent of the present invention reacts a cyclic acidic phosphate with sodium hydroxide to produce a compound represented by the general formula (1) in which M is a sodium atom.
- M is a sodium atom.
- it may be produced by adjusting P / Na to the above range using a known purification means, etc., and a compound in which M in the general formula (1) obtained by the above procedure is a sodium atom, although it can also manufacture by mixing the compound in which M in (1) is a hydrogen atom so that it may become the said ratio, it is not necessarily restricted to this.
- the nucleating agent of the present invention may be composed of only the compound represented by the general formula (1), and may contain known additives other than the compound represented by the general formula (1).
- the content of the compound represented by the general formula (1) is preferably 1 to 100% by mass, and more preferably 10 to 100% by mass.
- the polyolefin resin composition of the present invention contains 0.001 to 10 parts by mass of the nucleating agent of the present invention with respect to 100 parts by mass of the polyolefin resin. If it is less than 0.001 part by mass, the effect as a nucleating agent is insufficient, and if it exceeds 10 parts by mass, there is a risk of bleeding out on the surface of a molded product obtained by molding the polyolefin resin composition. There is.
- the amount is preferably 0.005 to 8 parts by mass, more preferably 0.01 to 5 parts by mass.
- polyolefin resin used in the polyolefin resin composition of the present invention examples include low density polyethylene, linear low density polyethylene, high density polyethylene, isotactic polypropylene, syndiotactic polypropylene, hemiisotactic polypropylene, ⁇ -olefin polymer such as cycloolefin polymer, stereoblock polypropylene, poly-3-methyl-1-butene, poly-3-methyl-1-pentene, poly-4-methyl-1-pentene, ethylene / propylene block or Examples include ⁇ -olefin copolymers such as random copolymers.
- polypropylene-based resins in which the use effect of the nucleating agent of the present invention is remarkable are preferable, and polypropylene, ethylene / propylene block or random copolymer, ⁇ -olefin / propylene other than ethylene Block or random copolymers and mixtures of these propylene-based polymers with other ⁇ -olefin polymers can also be used.
- these polyolefin resins having a melt flow rate in the range of 1 to 100 g / 10 min are preferably used because the effects of the present invention can be obtained satisfactorily, and the melt flow rate is 2 to 60 g / 10 min. Polyolefin resins that are within the range are particularly preferred.
- the production method of polyolefin resin includes Ziegler catalyst, Ziegler-Natta catalyst, metallocene catalyst and other various polymerization catalysts, including co-catalyst, catalyst carrier, chain transfer agent, gas phase polymerization, solution polymerization, emulsion polymerization, bulk
- various polymerization methods such as polymerization, it is possible to obtain resins having physical properties suitable for packaging materials, such as various polymerization conditions such as temperature, pressure, concentration, flow rate and removal of catalyst residues, and physical properties suitable for molding processing of packaging materials. It is produced by appropriately selecting a resin that can be obtained.
- Number average molecular weight, weight average molecular weight, molecular weight distribution, melt flow rate, melting point, melting peak temperature, isotacticity, syndiotactic and other stereoregularity of polyolefin resin, presence or absence of branching, specific gravity, dissolution in various solvents The ratio of components, haze, gloss, impact strength, flexural modulus, olsen stiffness, other characteristics, and whether each characteristic value satisfies a specific formula can be appropriately selected according to desired characteristics.
- polyolefin-based resin composition of the present invention other conventionally known additives that are generally used may be added as necessary as long as the effects of the present invention are not impaired.
- additives include neopentyl glycol derivatives, polyalkylene glycols and derivatives thereof, plasticizers such as polyhydric alcohols and epoxy compounds of the derivatives; antioxidants composed of phenolic, phosphorus, sulfur, etc .; hindered amines A light stabilizer comprising a light stabilizer, an ultraviolet absorber, etc .; a hydrocarbon compound, a fatty acid compound, an aliphatic alcohol compound, an aliphatic ester compound, an aliphatic amide compound, an aliphatic carboxylic acid metal salt compound, or Other metal soap lubricants, heavy metal deactivators, cationic surfactants, anionic surfactants, nonionic surfactants, amphoteric surfactants, antistatic agents, halogen compounds, phosphate esters Compound; phosphoric acid amide compound; melamine compound; fluororesin or metal oxide; ) Flame retardants such as melamine phosphate, (poly) piperazine phosphate; fillers such as glass fiber
- phenolic antioxidants examples include 2,6-ditert-butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, stearyl (3,5-ditert-butyl-4-hydroxy). Phenyl) propionate, distearyl (3,5-ditert-butyl-4-hydroxybenzyl) phosphonate, tridecyl-3,5-ditert-butyl-4-hydroxybenzylthioacetate, thiodiethylenebis [(3,5- Di-tert-butyl-4-hydroxyphenyl) propionate], 4,4′-thiobis (6-tert-butyl-m-cresol), 2-octylthio-4,6-di (3,5-di-tert-butyl- 4-hydroxyphenoxy) -s-triazine, 2,2′-methylenebis (4-methyl-6-tert-butylphenol), bis [3,3-bi (4-Hydroxy-3
- phosphorus antioxidants include triphenyl phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tris (2,5-di-tert-butylphenyl) phosphite, and tris (nonylphenyl).
- Phosphite tris (dinonylphenyl) phosphite, tris (mono, dimixed nonylphenyl) phosphite, diphenyl acid phosphite, 2,2'-methylenebis (4,6-ditert-butylphenyl) octyl phosphite , Diphenyldecyl phosphite, diphenyloctyl phosphite, di (nonylphenyl) pentaerythritol diphosphite, phenyl diisodecyl phosphite, tributyl phosphite, tris (2-ethylhexyl) phosphite, tridecyl phosphite, trilauryl phosphite , Dibutyl acid phosphite, dilauryl acid phosphite, trilauryl
- sulfur-based antioxidants examples include dialkylthiodipropionates such as dilauryl, dimyristyl, myristylstearyl, and distearyl esters of thiodipropionic acid, and polyols such as pentaerythritol tetra ( ⁇ -dodecylmercaptopropionate). Examples include ⁇ -alkyl mercaptopropionic acid esters.
- the use amount of the sulfur-based antioxidant is preferably 0.001 to 10 parts by mass, more preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the polyolefin resin.
- hindered amine light stabilizer examples include 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl stearate, 2,2,6. , 6-tetramethyl-4-piperidylbenzoate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1, 2,3,4-butanetetracarboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, bis (2,2,6 , 6-Tetramethyl-4-piperidyl) .di (tridecyl) -1,2,3,4-butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4- Peridyl) .di (tridecyl) -1
- ultraviolet absorber examples include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, and 5,5′-methylenebis (2-hydroxy-4-methoxybenzophenone).
- 2-hydroxybenzophenones such as 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2-hydroxy-3,5 -Di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3,5- Dicumylphenyl) benzotriazole, 2,2'-methylenebis (4-tertiary Octyl-6-benzotriazolylphenol), polyethylene glycol ester of 2- (2-hydroxy-3-tert-butyl-5-carboxyphenyl) benzotriazole, 2- [2-hydroxy-3- (2-acryloyloxy) Ethyl) -5-methylphenyl] benzotriazole, 2- [2-hydroxy-3- (2-methacryloyloxyethyl) -5-ter
- Examples of the aliphatic amide compound used as a lubricant include monofatty acid amides such as lauric acid amide, stearic acid amide, oleic acid amide, erucic acid amide, ricinoleic acid amide, and 12-hydroxystearic acid amide; N, N ′ -Ethylene bis lauric acid amide, N, N'-methylene bis stearic acid amide, N, N'-ethylene bis stearic acid amide, N, N'-ethylene bis oleic acid amide, N, N'-ethylene bis behenic acid amide N, N′-ethylenebis-12-hydroxystearic acid amide, N, N′-butylene bisstearic acid amide, N, N′-hexamethylene bisstearic acid amide, N, N′-hexamethylene bisoleic acid amide N, N′-bis such as N, N′-xylylenebisstearic acid amide Fatty acid amides; alky
- nucleating agents include, for example, sodium benzoate, 4-tert-butylaluminum benzoate aluminum salt, sodium adipate and disodium bicyclo [2.2.1] heptane-2,3-dicarboxylate Acid metal salt, sodium bis (4-tert-butylphenyl) phosphate, hydroxyaluminum bis [2,2′-methylenebis (4,6-ditert-butylphenyl) phosphate], and lithium-2,2′-methylenebis ( 4,6-ditertiarybutylphenyl) phosphate metal salts such as phosphate, dibenzylidene sorbitol, bis (methylbenzylidene) sorbitol, bis (p-ethylbenzylidene) sorbitol, and bis (dimethylbenzylidene) sorbitol Alcohol derivatives, N, N ', N "- Lis [2-methylcyclohexyl] -1,2,3-propanetricar
- the method of blending the polyolefin resin with the nucleating agent of the present invention is not particularly limited, and can be performed by a conventionally known method.
- polyolefin resin powder or pellets and the nucleating agent of the present invention may be mixed by dry blending, and after pre-blending a part of the nucleating agent of the present invention, dry blending with the remaining components. Good.
- mixing may be performed using a mill roll, a Banbury mixer, a super mixer, or the like, and kneading may be performed using a single screw or twin screw extruder.
- This mixing and kneading is usually performed at a temperature of about 120 to 250 ° C.
- a method of adding this one-pack composite additive to a polyolefin resin, a master batch containing the nucleating agent of the present invention at a high concentration, and a method of adding this master batch to a polyolefin resin. be able to.
- the molded product of the present invention is obtained by molding the polyolefin resin composition of the present invention.
- injection molding, extrusion molding, and blow molding are preferable.
- the molded product of the present invention include injection molded products, fibers, flat yarns, biaxially stretched films, uniaxially stretched films, unstretched films, sheets, thermoformed products, extrusion blow molded products, injection blow molded products, and injection stretched.
- the olefin-based resin composition of the present invention is used for various applications such as building materials, agricultural materials, vehicle parts such as automobiles, trains, ships, and aircraft, packaging materials, miscellaneous goods, toys, home appliances, and medical products. be able to.
- automotive parts such as bumpers, dashboards, instrument panels, battery cases, luggage cases, door panels, door trims, fender liners; resin parts for household appliances such as refrigerators, washing machines, vacuum cleaners; tableware, bottles Household goods such as caps, buckets, bathing goods, etc .; resin parts for connection such as connectors; miscellaneous goods such as toys, storage containers, synthetic papers; medical packs, syringes, catheters, medical tubes, syringe preparations, infusion bags, reagents Medical molded products such as containers, pill containers, and individual pill packaging; building materials such as walls, flooring, window frames, wallpaper, and windows; wire covering materials; agricultural materials such as houses, tunnels, and flat yarn mesh bags Pallets, pail cans, back grind tapes, LCD protective tapes, pipes, modified silicone polymers for sealing materials Industrial materials of; wrap, trays, cups, films, bottles, caps, food packaging, such as storage containers, and other 3D printers materials include battery separator film.
- low-temperature plasma is applied after molding to improve surface properties such as application for various post-treatments, for example, medical applications, food packaging applications, etc., or sterilization by radiation. It can be used for purposes such as processing. Among these, it is preferable to use for automobile parts, household goods, and food packaging materials.
- the polyolefin resin composition of the present invention may be a fiber reinforced plastic by blending glass fibers, carbon fibers and the like.
- the preferable molding temperature is in the range of 120 to 250 ° C, more preferably in the range of 130 to 240 ° C. If the temperature is lower than 120 ° C., the polyolefin resin itself cannot be sufficiently dissolved, and there is a possibility that the molded product may be uneven. If the temperature is 250 ° C. or higher, the effects of the present invention may not be obtained.
- ⁇ Synthesis of nucleating agent 2 A solution of 486 g (1.000 mol) of 2,2′-methylenebis (4,6-di-t-butylphenyl) phosphate, 40 g (1.000 mol) of sodium hydroxide and 100 g of water and 97 g of methanol are charged into a kneader. And kneading for 1 hour at room temperature. Thereto was added 14 g (0.350 mol) of sodium hydroxide, mixed for 30 minutes, dried under reduced pressure and pulverized to obtain a nucleating agent 2 as a white powder.
- nucleating agent 3 A solution of 486 g (1.000 mol) of 2,2′-methylenebis (4,6-di-t-butylphenyl) phosphate, 40 g (1.000 mol) of sodium hydroxide and 100 g of water and 97 g of methanol are charged into a kneader. And kneading for 1 hour at room temperature. To this, 199 g (0.409 mol) of 2,2′-methylenebis (4,6-di-t-butylphenyl) phosphate was added, mixed for 30 minutes, dried under reduced pressure and pulverized to produce a white powder. Nucleating agent 3 was obtained.
- nucleating agent 4 A solution of 486 g (1.000 mol) of 2,2′-methylenebis (4,6-di-t-butylphenyl) phosphate, 40 g (1.000 mol) of sodium hydroxide and 100 g of water and 97 g of methanol are charged into a kneader. And kneading for 1 hour at room temperature. Thereto was added 1 g (0.002 mol) of 2,2′-methylenebis (4,6-di-t-butylphenyl) phosphate, mixed for 30 minutes, dried under reduced pressure and pulverized to produce a white powder. Nucleating agent 4 was obtained.
- nucleating agent 7 A solution of 486 g (1.000 mol) of 2,2′-methylenebis (4,6-di-t-butylphenyl) phosphate, 40 g (1 mol) of sodium hydroxide and 100 g of water and 97 g of methanol were charged in a kneader. And kneading for 1 hour. Thereto was added 55 g (0.113 mol) of 2,2′-methylenebis (4,6-di-t-butylphenyl) phosphate, mixed for 30 minutes, dried under reduced pressure and pulverized to produce a white powder. Nucleating agent 7 was obtained.
- ⁇ Bending elastic modulus> The obtained pellets were injection molded with an injection molding machine (EC100-2A; manufactured by Toshiba Machine Co., Ltd.) under the conditions of an injection temperature of 200 ° C. and a mold temperature of 50 ° C., and a test with dimensions of 80 mm ⁇ 10 mm ⁇ 4 mm. A piece was prepared and immediately put into a thermostat at 23 ° C. and allowed to stand for 48 hours. Then, the test piece was taken out and the flexural modulus (MPa) of the test piece was measured according to ISO-178. The obtained results are also shown in Table 2.
- MPa flexural modulus
- the nucleating agent of the present invention can improve the transparency and heat resistance of a molded product made of a polyolefin resin composition.
- P / Na is 1.350, 1.400, and 1.450
- Y.I. I It can be seen that the value of is 6 units, the value of Haze is 51 units, and the storage stability at 150 ° C. is good.
Abstract
Description
(一般式(1)中、R1~R4は各々独立して、水素原子、直鎖または分岐を有していてもよい炭素原子数1~9のアルキル基を表し、R5は炭素原子数1~4のアルカンジイル基を表し、Mは水素原子またはナトリウム原子を表す)で表される化合物を含有する造核剤において、
前記造核剤中のリン原子とナトリウム原子との質量比P/Naが1.200~1.500の範囲であることを特徴とするものである。
本発明の造核剤は、下記一般式(1)、
で表される化合物を含有する造核剤である。ここで、一般式(1)中、R1~R4は各々独立して、水素原子、直鎖または分岐を有していてもよい炭素原子数1~9のアルキル基を表し、R5は炭素原子数1~4のアルカンジイル基を表し、Mは水素原子またはナトリウム原子を表す。
本発明のポリオレフィン系樹脂組成物は、ポリオレフィン系樹脂100質量部に対して、本発明の造核剤が0.001~10質量部含有されてなる。0.001質量部未満であると、造核剤としての効果が不十分であり、10質量部より多いと、ポリオレフィン系樹脂組成物を成形加工して得られる成形品の表面にブリードアウトするおそれがある。好ましくは0.005~8質量部、より好ましくは、0.01~5質量部配合される。
ホモポリプロピレン(株式会社プライムポリマー社製品名「H700」,メルトフローレート=8g/10min(ISO規格1133準拠 2.16kg×230℃))100質量部に対し、フェノール系酸化防止剤(テトラキス[メチレン-3-(3’,5’-ジ-tert-ブチル-4’-ヒドロキシフェニル)プロピオネート]メタン)0.05質量部、リン系酸化防止剤(トリス(2,4-ジ-tert-ブチルフェニル)ホスファイト)0.1質量部、ステアリン酸カルシウム0.05質量部、および、表2に記載の有機リン酸エステル化合物(造核剤)0.1質量部を配合し、ヘンシェルミキサー(三井鉱山製、FM100)で、1000rpm×1min混合後、二軸押出機(日本製鋼所製、TEX28V)を用いて、押出温度=230℃、スクリュー回転速度=150rpm、フィード速度=7.5kg/hの条件で混練し、ペレットを製造した。得られた樹脂組成物を用いて、下記の手順に従って、黄色度(Y.I.)、Haze、曲げ弾性率および150℃保存時耐熱性の評価を行った。なお、各造核剤の製造方法、およびP/Naの測定は以下の手順で行った。
2,2’-メチレンビス(4,6-ジ-t-ブチルフェニル)ホスフェート486g(1.000モル)、水酸化ナトリウム40g(1.000モル)と水100gの溶液およびメタノール97gをニーダー中に仕込み、室温で一時間混練した。そこに2,2’-メチレンビス(4,6-ジ-t-ブチルフェニル)ホスフェート19g(0.039モル)を加え、30分混合した後、減圧下に乾燥した後粉砕し、白色粉末の造核剤1を得た。
2,2’-メチレンビス(4,6-ジ-t-ブチルフェニル)ホスフェート486g(1.000モル)、水酸化ナトリウム40g(1.000モル)と水100gの溶液およびメタノール97gをニーダー中に仕込み、室温で一時間混練した。そこに水酸化ナトリウム14g(0.350モル)を加え、30分混合した後、減圧下に乾燥した後粉砕し、白色粉末の造核剤2を得た。
2,2’-メチレンビス(4,6-ジ-t-ブチルフェニル)ホスフェート486g(1.000モル)、水酸化ナトリウム40g(1.000モル)と水100gの溶液およびメタノール97gをニーダー中に仕込み、室温で一時間混練した。そこに2,2’-メチレンビス(4,6-ジ-t-ブチルフェニル)ホスフェート199g(0.409モル)を加え、30分混合した後、減圧下に乾燥した後粉砕し、白色粉末の造核剤3を得た。
2,2’-メチレンビス(4,6-ジ-t-ブチルフェニル)ホスフェート486g(1.000モル)、水酸化ナトリウム40g(1.000モル)と水100gの溶液およびメタノール97gをニーダー中に仕込み、室温で一時間混練した。そこに2,2’-メチレンビス(4,6-ジ-t-ブチルフェニル)ホスフェート1g(0.002モル)を加え、30分混合した後、減圧下に乾燥した後粉砕し、白色粉末の造核剤4を得た。
2,2’-メチレンビス(4,6-ジ-t-ブチルフェニル)ホスフェート486g(1.000モル)、水酸化ナトリウム40g(1.000モル)と水100gの溶液およびメタノール97gをニーダー中に仕込み、室温で一時間混練した。そこに2,2’-メチレンビス(4,6-ジ-t-ブチルフェニル)ホスフェート37g(0.076モル)を加え、30分混合した後、減圧下に乾燥した後粉砕し、白色粉末の造核剤5を得た。
2,2’-メチレンビス(4,6-ジ-t-ブチルフェニル)ホスフェート486g(1.000モル)、水酸化ナトリウム40g(1.000モル)と水100gの溶液およびメタノール97gをニーダー中に仕込み、室温で一時間混練した。そこに水酸化ナトリウム1.48g(0.037モル)を加え、減圧下に乾燥した後粉砕し、白色粉末の造核剤6を得た。
2,2’-メチレンビス(4,6-ジ-t-ブチルフェニル)ホスフェート486g(1.000モル)、水酸化ナトリウム40g(1モル)と水100gの溶液およびメタノール97gをニーダー中に仕込み、室温で一時間混練した。そこに2,2’-メチレンビス(4,6-ジ-t-ブチルフェニル)ホスフェート55g(0.113モル)を加え、30分混合した後、減圧下に乾燥した後粉砕し、白色粉末の造核剤7を得た。
各造核剤を100mg秤量し、そこに61%硝酸を10ml加えてマイクロウェーブ試料分解装置(TOPwave:Analytik jena AG)にて分解する。分解溶液を100mlにメスアップ後10倍希釈し、孔径0.45μmのディスポーザブルメンブレンフィルターを用いてろ過し、測定用試料溶液を調整した。その後、ICP発光分光分析装置(SPS3500:SII)で下記条件にて測定用試料溶液中のPおよびNaを定量し、その結果からNA-11サンプル中のP/Naを算出した。
得られたペレットを、射出成形機(EC100-2A;東芝機械株式会社製)にて、200℃で射出成形した。寸法60mm×60mm×2mmの試験片を作製した。成形後、直ちに23℃の恒温機にいれて48時間静置後、試験片を取り出して分光測色計(Color-Eye 7000A:X-rite社製)により試験片のY.I.を測定した。得られた結果を表2に併記する。
得られたペレットを、射出成形機(EC100-2A;東芝機械株式会社製)にて、200℃の射出温度、50℃の金型温度の条件で射出成形し、寸法60mm×60mm×2mmの試験片を作成し、成形後直ちに23℃の恒温機にいれて48時間静置後、試験片を取り出してISO-14782に準拠して試験片のHazeを測定した。得られた結果を表2に併記する。
得られたペレットを、射出成形機(EC100-2A;東芝機械株式会社製)にて、200℃の射出温度、50℃の金型温度の条件で射出成形し、寸法80mm×10mm×4mmの試験片を作成し、成形後直ちに23℃の恒温機にいれて48時間静置後、試験片を取り出してISO-178に準拠して試験片の曲げ弾性率(MPa)を測定した。得られた結果を表2に併記する。
得られた試験片を150℃のギヤーオーブン内に静置した。静置後、24時間毎に試験片を取り出して、顕微鏡観察によるクラックの有無の確認およびY.I.測定を実施した。クラック発生およびY.I.上昇までの耐久時間が550時間~600時間の場合を○、500時間~550時間の場合を△とした。得られた結果を表2に併記する。
Claims (4)
- 前記造核剤中のリン原子とナトリウム原子との質量比P/Naが1.350~1.450の範囲である請求項1記載の造核剤。
- ポリオレフィン系樹脂100質量部に対して、請求項1または2記載の造核剤が0.001~10質量部含有されてなることを特徴とするポリオレフィン系樹脂組成物。
- 請求項3記載のポリオレフィン系樹脂組成物が成形されてなることを特徴とする成形品。
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US16/969,404 US11306194B2 (en) | 2018-02-13 | 2019-02-04 | Nucleating agent, polyolefin-based resin composition containing same, and molded article thereof |
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- 2019-02-04 BR BR112020016348-1A patent/BR112020016348B1/pt active IP Right Grant
- 2019-02-04 CN CN201980013019.0A patent/CN111712539A/zh active Pending
- 2019-02-13 TW TW108104710A patent/TWI728311B/zh active
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2020
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2022
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Also Published As
Publication number | Publication date |
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JP6756944B2 (ja) | 2020-09-16 |
BR112020016348A2 (pt) | 2020-12-15 |
SA520412627B1 (ar) | 2022-10-30 |
RU2758474C1 (ru) | 2021-10-28 |
EP3747944A1 (en) | 2020-12-09 |
JPWO2019159743A1 (ja) | 2020-08-20 |
BR112020016348B1 (pt) | 2022-07-12 |
US20210047498A1 (en) | 2021-02-18 |
TW201940495A (zh) | 2019-10-16 |
TWI728311B (zh) | 2021-05-21 |
CN111712539A (zh) | 2020-09-25 |
JP2021004359A (ja) | 2021-01-14 |
KR20200120635A (ko) | 2020-10-21 |
US11306194B2 (en) | 2022-04-19 |
US20220204724A1 (en) | 2022-06-30 |
CN108384053A (zh) | 2018-08-10 |
EP3747944B1 (en) | 2022-06-15 |
EP3747944A4 (en) | 2021-04-07 |
KR20220021016A (ko) | 2022-02-21 |
KR102510746B1 (ko) | 2023-03-15 |
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