WO2018150755A1 - Nouveau composé, agent de nucléation, composition de résine et article moulé - Google Patents

Nouveau composé, agent de nucléation, composition de résine et article moulé Download PDF

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Publication number
WO2018150755A1
WO2018150755A1 PCT/JP2017/047339 JP2017047339W WO2018150755A1 WO 2018150755 A1 WO2018150755 A1 WO 2018150755A1 JP 2017047339 W JP2017047339 W JP 2017047339W WO 2018150755 A1 WO2018150755 A1 WO 2018150755A1
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tert
group
nucleating agent
butyl
acid
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PCT/JP2017/047339
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English (en)
Japanese (ja)
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崇史 武藤
満 友田
和清 野村
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株式会社Adeka
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C243/00—Compounds containing chains of nitrogen atoms singly-bound to each other, e.g. hydrazines, triazanes
    • C07C243/24—Hydrazines having nitrogen atoms of hydrazine groups acylated by carboxylic acids
    • C07C243/38—Hydrazines having nitrogen atoms of hydrazine groups acylated by carboxylic acids with acylating carboxyl groups bound to carbon atoms of six-membered aromatic rings
    • 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
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/22—Compounds containing nitrogen bound to another nitrogen atom
    • C08K5/24—Derivatives of hydrazine
    • C08K5/25—Carboxylic acid hydrazides
    • 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

Definitions

  • the present invention relates to a novel metal salt of a dicarboxylic acid hydrazide compound useful as a nucleating agent for polyolefin resins. Furthermore, the present invention relates to a nucleating agent containing the novel compound, a polyolefin-based resin composition containing the nucleating agent, and a molded article comprising the composition. About.
  • Polyolefin-based resins such as polyethylene, polypropylene, and polybutene-1 have advantages such as molding processability, heat resistance, electrical properties, mechanical properties, and low specific gravity, and film molding, sheet molding, blow molding, Widely used in various fields as a material for injection molding.
  • polyolefin resins have problems such as a slow crystallization rate after heat molding and a long molding cycle during processing.
  • the molded product may be deformed by crystallization that proceeds after molding.
  • a nucleating agent or crystallization accelerator
  • Effective compounds as nucleating agents for polyolefin resins include sodium adipate, potassium adipate, aluminum adipate, sodium sebacate, potassium sebacate, aluminum sebacate, sodium benzoate, potassium benzoate, lithium benzoate, benzoate Aluminum oxide, aluminum di-para-t-butylbenzoate, titanium di-para-t-butylbenzoate, chromium di-para-t-butylbenzoate, aluminum hydroxy-di-t-butylbenzoate, ⁇ -naphtho Metal salt types such as sodium acid, sodium cyclohexanecarboxylate, sodium cyclopentanecarboxylate, sodium bis (4-tert-butylphenyl) phosphate, sodium 2,2′-methylenebis (4,6-di-ter Phosphate metal salt types such as -butylphenyl) phosphate and lithium-2,2'-methylenebis (4,6-di-tert-butylpheny
  • nucleating agents Although these various nucleating agents are known, they satisfy all requirements such as effective concentration, dispersibility in polyolefin resin, influence on color tone and moldability of polyolefin resin, price, and handleability. There are few nucleating agents, and each nucleating agent has advantages and disadvantages. For this reason, the development of new nucleating agents continues. For example, an organic carboxylic acid metal salt type nucleating agent is advantageous over a sorbitol type nucleating agent at a single price, but may be inferior to other nucleating agents in terms of dispersibility in a polymer and crystallization promoting effect.
  • Patent Document 1 discloses di-sodium bicyclo [2.2.1] heptane-2,3-dicarboxylate, calcium bicyclo [2.2. 1] It is described that a bicyclic compound such as heptane-2,3-dicarboxylate exhibits a crystallization promoting effect superior to a conventionally used nucleating agent such as calcium stearate.
  • Patent Document 2 discloses that a composition comprising a combination of cis-2 sodium hexahydrophthalate and an acid supplement is more effective in promoting crystallization than a combination of a conventional nucleating agent such as sodium benzoate and an acid supplement. Is described.
  • Patent Document 3 by the present applicant describes that a hydrazide compound having a cyclohexyl group or a phenyl group functions as a nucleating agent for polyolefin resin.
  • a crystal nucleating agent selected from the group consisting of metal salts of aromatic organophosphates, dibenzylidene sorbitol derivatives, carboxylic acid metal salts, rosin acid partial metal salts, and talc is water-soluble ionic. It is described that a composition supported on an inorganic powder containing a copolymer exhibits a nucleating agent effect while maintaining the mechanical properties of a polyolefin-based resin.
  • the second object of the present invention is to provide a polyolefin resin composition having a high added value as a molding material in which a more excellent nucleating agent is blended.
  • the inventors of the present invention blend a metal salt of a specific dicarboxylic acid hydrazide compound, which is a novel compound that is not disclosed in the above-mentioned patent documents, with a polyolefin resin.
  • a polyolefin-based resin composition with improved crystallinity was obtained, and the present invention was completed. That is, the present invention is as follows.
  • (Invention 1) A compound represented by the following formula (1).
  • Ring A and Ring B represent an aryl group having 6 to 20 carbon atoms or a cycloalkyl group having 3 to 20 carbon atoms
  • M represents an alkali metal atom
  • the group may be substituted with a hydroxyl group, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms and an alkenyl group having 2 to 10 carbon atoms.
  • the alkyl group therein may be interrupted by a carbonyl group or an oxygen atom, and may have an unsaturated bond.
  • (Invention 2) The compound according to (Invention 1) represented by the following formula (2).
  • M represents an alkali metal atom
  • R 1 to R 9 each independently represents a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or 1 to 10 represents an alkoxy group, an alkenyl group having 2 to 10 carbon atoms, and the alkyl group or the alkyl group in the alkoxy group may be interrupted by a carbonyl group or an oxygen atom, and has an unsaturated bond. May be good.
  • (Invention 3) A nucleating agent containing the compound represented by the formula (1) or (2).
  • invention 4 A polyolefin resin and the nucleating agent according to (3), wherein the total amount of one or more compounds represented by the above formula (1) or the above formula (2) is 100 mass of the above polyolefin resin.
  • a polyolefin-based resin composition in the range of 0.0001 to 10 parts by mass with respect to parts.
  • the novel compound which can provide the resin composition which has the outstanding nucleating agent effect and has little anisotropy of shrinkage
  • the compound of the present invention is a novel compound and useful as a nucleating agent for thermoplastic resins including polyolefin resins.
  • a nucleating agent compound such a compound of the present invention is referred to as a “nucleating agent compound”.
  • This nucleating agent compound is a metal salt of a dicarboxylic acid hydrazide compound represented by the following general formula (1).
  • ring A and ring B represent an aryl group having 6 to 20 carbon atoms or a cycloalkyl group having 3 to 20 carbon atoms
  • M represents an alkali metal atom
  • an aryl group or a cycloalkyl group May be substituted with a hydroxyl group, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms and an alkenyl group having 2 to 10 carbon atoms.
  • the alkyl group may be interrupted by a carbonyl group or an oxygen atom, and may have an unsaturated bond.
  • Examples of the aryl group having 6 to 20 carbon atoms of the ring A and the ring B in the formula (1) include phenyl, naphthyl, biphenyl, anthracenyl and the like, and the hydrogen atom of the aryl group is a hydroxyl group, a halogen atom, a carbon atom. It may be substituted with an alkyl group having 1 to 10 atoms, an alkoxy group having 1 to 10 carbon atoms, and an alkenyl group having 2 to 10 carbon atoms.
  • Examples of the cycloalkyl group having 3 to 20 carbon atoms of the ring A and the ring B in the formula (1) include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and the like.
  • the hydrogen atom of the cycloalkyl group is a hydroxyl group, a halogen atom, It may be substituted with an atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and an alkenyl group having 2 to 10 carbon atoms.
  • alkyl group having 1 to 10 carbon atoms examples include linear or branched alkyl groups and cycloalkyl groups having 3 to 10 carbon atoms. Specifically, for example, methyl, ethyl, propyl, isopropyl, cyclopropyl, butyl, sec-butyl, tert-butyl, isobutyl, cyclobutyl, amyl, tert-amyl, cyclopentyl, hexyl, cyclohexyl, heptyl, cycloheptyl, octyl , Cyclooctyl, isooctyl, tert-octyl, 2-ethylhexyl, nonyl, isononyl, decyl and the like.
  • alkoxy group having 1 to 10 carbon atoms examples include linear or branched alkoxy groups and cycloalkoxy groups having 5 to 10 carbon atoms. Specific examples include methoxy, ethoxy, n-propoxy, n-butoxy, n-hexyloxy, 1-methylethoxy, 2-methylpropoxy, 1-methylbutoxy, 4-methylpentyloxy, cyclohexyloxy and the like. It is done.
  • alkenyl group having 2 to 10 carbon atoms examples include vinyl, allyl, propenyl, decenyl and the like.
  • the nucleating agent compound of the present invention is preferably a compound represented by the following formula (2).
  • M represents an alkali metal atom
  • R 1 to R 9 each independently represents a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or 1 to 10 carbon atoms.
  • Typical examples of such a nucleating agent compound of the present invention are compounds represented by the following formulas (3-1) to (3-16).
  • the nucleating agent compound of the present invention is obtained as a water-insoluble alkali metal salt by saponifying the precursor (4) corresponding to the compound represented by the formula (1) in an alkaline aqueous solution. it can.
  • R ′′ represents an alkyl group having 1 to 10 carbon atoms.
  • the precursor (4) can be synthesized according to the following reaction formula. That is, it can be easily synthesized by reacting hydrazine or a derivative thereof with a carboxyl group-containing compound or an acid halide.
  • R a is an aryl group having 6 to 20 carbon atoms or a cycloalkyl group having 3 to 20 carbon atoms corresponding to ring A in formula (1)
  • R b is a ring B in formula (1).
  • R ′ is a hydrocarbon group
  • R ′′ is an alkyl group having 1 to 10 carbon atoms
  • X is a halogen atom. .
  • the nucleating agent compound of the present invention is useful as a nucleating agent for polyolefin resins.
  • the nucleating agent of the present invention may be composed of the nucleating agent compound of the present invention, or may contain other additives in addition to the nucleating agent compound of the present invention.
  • limiting in particular in content of the nucleating agent compound in the nucleating agent of this invention Preferably it is 10 mass% or more with respect to the nucleating agent whole quantity, More preferably, it is 80 mass% or more.
  • the other additive combined with the nucleating agent compound is not limited as long as it is an additive that can be blended with the polyolefin resin. For example, one or more additives including known nucleating agents described later are used. Can do.
  • the polyolefin resin composition of the present invention is a composition comprising a polyolefin resin and the nucleating agent of the present invention.
  • the nucleating agent compound of the present invention is 0.0001 to 10 parts by mass with respect to 100 parts by mass of the polyolefin resin.
  • the nucleating agent of the present invention is blended with a polyolefin-based resin so as to have a concentration of 0.005 to 5 parts by mass, more preferably 0.01 to 0.5 parts by mass.
  • the concentration of the nucleating agent compound is less than 0.0001 parts by mass with respect to 100 parts by mass of the polyolefin resin, the effect of addition is insufficient, and if it is more than 10 parts by mass, the effect of the nucleating agent compound of the present invention as a nucleating agent May not be obtained.
  • polyolefin resin used in the polyolefin resin composition of the present invention examples include low density polyethylene (LDPE), linear low density polyethylene (L-LDPE), high density polyethylene (HDPE), isotactic polypropylene, Syndiotactic polypropylene, hemiisotactic polypropylene, cycloolefin polymer, stereoblock polypropylene, poly-3-methyl-1-butene, poly-3-methyl-1-pentene, poly-4-methyl-1-pentene, etc.
  • LDPE low density polyethylene
  • L-LDPE linear low density polyethylene
  • HDPE high density polyethylene
  • isotactic polypropylene Syndiotactic polypropylene
  • hemiisotactic polypropylene hemiisotactic polypropylene
  • cycloolefin polymer stereoblock polypropylene
  • poly-3-methyl-1-butene poly-3-methyl-1-pentene
  • ⁇ -olefin polymer ethylene / propylene block or random copolymer, impact copolymer polypropylene, ethylene-methyl methacrylate copolymer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer Body, ethylene - butyl acrylate copolymer, ethylene - vinyl acetate copolymer, ethylene - alpha-olefin copolymer such as polyvinyl alcohol resin (EVOH).
  • EVOH polyvinyl alcohol resin
  • these two or more types may be blended and used, a block copolymer may be formed and used as a block polymer type, or the resin may be alloyed. Further, chlorinated products of these polyolefin resins may be used.
  • the polyolefin resin elastomer is a polyolefin such as polypropylene or polyethylene as a hard segment, an elastomer such as ethylene-propylene rubber as a soft segment, and an elastomer obtained by blending these, or an elastomer obtained by dynamic crosslinking.
  • the hard segment include at least one selected from polypropylene homopolymer, polypropylene block copolymer, polypropylene random copolymer, and the like.
  • soft segment examples include ethylene-propylene copolymer (EPM), ethylene-propylene-diene copolymer (EPDM), ethylene-vinyl acetate copolymer (EVA), and vinyl acetate homopolymer. Two or more of these may be blended and used.
  • EPM ethylene-propylene copolymer
  • EPDM ethylene-propylene-diene copolymer
  • EVA ethylene-vinyl acetate copolymer
  • vinyl acetate homopolymer Two or more of these may be blended and used.
  • the polyolefin resin production method includes Ziegler catalyst, Ziegler-Natta catalyst, metallocene catalyst and other various polymerization catalysts as cocatalyst, catalyst carrier, chain transfer agent, gas phase polymerization, solution polymerization, emulsion polymerization,
  • resins with physical properties suitable for packaging materials such as temperature, pressure, concentration, flow rate and various polymerization conditions such as removal of catalyst residues can be obtained, and physical properties suitable for molding processing of packaging materials. It is produced by appropriately selecting a resin that can be obtained.
  • the ratio of dissolved components, haze, gloss, impact strength, flexural modulus, olsen stiffness, other characteristics, and whether each characteristic value satisfies a specific formula, etc. can be appropriately selected according to the desired characteristics. it can.
  • any known resin additive for example, a phenol-based antioxidant, a phosphorus-based antioxidant, a thioether-based antioxidant, and the like, as long as the effects of the present invention are not significantly impaired
  • Antioxidants, hindered amine compounds, UV absorbers, other nucleating agents, flame retardants, flame retardant aids, lubricants, fillers, hydrotalcites, fatty acid metal salts, antistatic agents, pigments, dyes, etc. You may let them.
  • phenolic antioxidant examples include 2,6-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-ethylphenol, and 2-tert-butyl-4,6-dimethyl.
  • tetrakis [methylene-3- (3 ′, 5′-tert-butyl-4′-hydroxyphenyl) propionate] methane is preferable because it is inexpensive and has an excellent stabilizing effect on the polypolyolefin resin.
  • the blending amount is preferably 0.001 to 5 parts by weight and more preferably 0.01 to 1.0 part by weight with respect to 100 parts by weight of the polyolefin resin.
  • Phosphorous antioxidants include, for example, triphenyl phosphite, diisooctyl phosphite, heptakis (dipropylene glycol) triphosphite, triisodecyl phosphite, diphenylisooctyl phosphite, diisooctylphenyl phosphite, diphenyltri Decyl phosphite, triisooctyl phosphite, trilauryl phosphite, diphenyl phosphite, tris (dipropylene glycol) phosphite, diisodecyl pentaerythritol diphosphite, dioleyl hydrogen phosphite, trilauryl trithiophosphite, bis ( Tridecyl) phosphite, tris (isodecyl) phosphit
  • thioether-based antioxidant examples include 3,3′-thiodipropionic acid, alkyl (C12-14) thiopropionic acid, di (lauryl) -3,3′-thiodipropionate, and di (tridecyl) -3.
  • antioxidants include, for example, N-benzyl- ⁇ -phenylnitrone, N-ethyl- ⁇ -methylnitrone, N-octyl- ⁇ -heptylnitrone, N-lauryl- ⁇ -undecylnitrone, N-tetradecyl- ⁇ -tridecylnitrone, N-hexadecyl- ⁇ -pentadecylnitrone, N-octyl- ⁇ -heptadecylnitrone, N-hexadecyl- ⁇ -heptadecylnitrone, N-octadecyl- ⁇ -pentadecylnitrone, N-heptadecyl- Nitron compounds such as ⁇ -heptadecylnitrone and N-octadecyl- ⁇ -heptadecylnitrone, 3-arylbenzofuran-2 (3H) -one, 3- (al
  • hindered amine compounds include 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl stearate, 2,2,6,6-tetra Methyl-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-tetra Methyl-4-piperidyl) -di (tridecyl) -1,2,3,4-butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) Di (tridecyl) -1,2,3,
  • the blending amount is preferably 0.001 to 5 parts by mass, more preferably 0.005 to 0.5 parts by mass with respect to 100 parts by mass of the polyolefin resin.
  • Examples of the ultraviolet absorber include 2-hydroxybenzophenones such as 2,4-dihydroxybenzophenone and 5,5′-methylenebis (2-hydroxy-4-methoxybenzophenone); 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-tert-octyl) -6-benzotriazolylphenol), 2- (2-hydroxy-3 tert-butyl-5-carboxyphenyl) benzotriazole polyethylene glycol ester, 2- [2-hydroxy-3- (2-acryloyloxyethy
  • the blending amount in the case of blending the ultraviolet absorber is preferably 0.001 to 5 parts by mass, more preferably 0.005 to 0.5 parts by mass with respect to 100 parts by mass of the polyolefin resin.
  • nucleating agents different from the nucleating agent of the present invention include, for example, sodium-2,2′-methylenebis (4,6-di-tert-butylphenyl) phosphate, lithium-2,2′-methylenebis (4,6 -Di-tert-butylphenyl) phosphate, aluminum hydroxybis [2,2'-methylenebis (4,6-di-tert-butylphenyl) phosphate], sodium benzoate, 4-tert-butylaluminum benzoate aluminum salt, adipine Carboxylic acid metal salts such as sodium and disodium bicyclo [2.2.1] heptane-2,3-dicarboxylate, dibenzylidene sorbitol, bis (methylbenzylidene) sorbitol, bis (3,4-dimethylbenzylidene) sorbitol Bis (p-ethylbenzylidene) sorbitol, And polyol derivatives such as bis (di
  • the total amount with the nucleating agent of the present invention is preferably 0.05 to 10 parts by mass with respect to 100 parts by mass of the polyolefin resin, and 0.01 to 0.001. 5 parts by mass is more preferable.
  • Examples of the flame retardant include triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, cresyl-2,6-dixylenyl phosphate, resorcinol bis (diphenyl phosphate), (1-methylethylidene)- 4,1-phenylenetetraphenyldiphosphate, 1,3-phenylenetetrakis (2,6-dimethylphenyl) phosphate, trade name ADEKA STAB (registered trademark) FP-500 manufactured by ADEKA Corporation, trade name ADEKA STAB (trade name) manufactured by ADEKA Corporation (Trademark) FP-600, ADEKA Corporation trade name ADK STAB (registered trademark) FP-800, etc., aromatic phosphate ester, phenylphosphonate divinyl, phenylphosphonate diallyl, phenylphosphonic acid (1-buteni
  • flame retardants are preferably used in combination with anti-drip agents such as fluororesins and flame retardant aids such as polyols and hydrotalcites.
  • the blending amount when the flame retardant is blended is preferably 1 to 50 parts by weight and more preferably 10 to 30 parts by weight with respect to 100 parts by weight of the polyolefin resin.
  • the lubricant is added for the purpose of imparting lubricity to the surface of the molded body and enhancing the damage prevention effect.
  • the lubricant include hydrocarbon lubricants such as low molecular wax, paraffin wax, polyethylene wax, chlorinated hydrocarbon, and fluorocarbon; natural wax lubricants such as carnauba wax and candeli wax; lauric acid, stearic acid, and behenic acid Fatty acid lubricants such as higher fatty acids such as oxyfatty acids such as hydroxystearic acid; aliphatic amide compounds such as stearylamide, laurylamide, oleylamide, or alkylenebisfats such as methylenebisstearylamide, ethylenebisstearylamide Aliphatic amide-based lubricants such as aliphatic amide compounds; fatty acid monohydric alcohol ester compounds such as stearyl stearate, butyl stearate, distearyl phthalate; glycerin tristearate
  • Fillers include, for example, talc, mica, calcium carbonate, calcium oxide, calcium hydroxide, magnesium carbonate, magnesium hydroxide, magnesium oxide, magnesium sulfate, aluminum hydroxide, barium sulfate, glass powder, glass fiber, clay, dolomite, Mica, silica, alumina, potassium titanate whisker, wollastonite, fibrous magnesium oxysulfate and the like can be mentioned, and the particle diameter (in the fibrous form, fiber diameter, fiber length and aspect ratio) can be appropriately selected and used. it can. Moreover, what was surface-treated as needed can be used for a filler.
  • Hydrotalcite is a natural product or a synthetic product. It is a complex salt compound consisting of magnesium, aluminum, hydroxyl group, carbonate group and any water of crystallization known as, which is obtained by substituting a part of magnesium or aluminum with other metals such as alkali metal or zinc, or other hydroxyl group or carbonate group And those substituted with an anionic group.
  • Such hydrosites are typically alkali metal-substituted hydrotalcites represented by the following formula (5) or Al—Li hydrotalcites represented by the following formula (6): It is kind.
  • X1 and X2 represent numbers satisfying the conditions: 0 ⁇ X2 / X1 ⁇ 10, 2 ⁇ X1 + X2 ⁇ 20, and p represents 0 or a positive number.
  • a q ⁇ represents a q-valent anion
  • p represents 0 or a positive number.
  • the carbonate anion in the hydrotalcite may be partially substituted with another anion.
  • Hydrotalcite may be obtained by dehydrating crystallization water, higher fatty acid such as stearic acid, higher fatty acid metal salt such as alkali metal oleate, organic sulfonic acid metal such as alkali metal dodecylbenzenesulfonate. It may be coated with a salt, higher fatty acid amide, higher fatty acid ester or wax.
  • Hydrotalcites may be natural products or synthetic products. As synthesis methods, Japanese Patent Publication No. 46-2280, Japanese Patent Publication No. 50-30039, Japanese Patent Publication No. 51-29129, Japanese Patent Publication No. 3-36839, Japanese Patent Publication No. 61-174270, Japanese Patent Publication No. Hei 5- The publicly known method described in 179052 gazette etc. is mentioned. Hydrotalcites can be used without being limited by their crystal structure, crystal particles, and the like. When the hydrotalcite is blended, the blending amount is preferably 0.001 to 5 parts by mass, more preferably 0.05 to 3 parts by mass with respect to 100 parts by mass of the polyolefin resin.
  • Fatty acid metal salts include, for example, capric acid, 2-ethylhexanoic acid, undecylic acid, lauric acid, tridecylic acid, myristic acid, pentadecylic acid, palmitic acid, margaric acid, stearic acid, nonadecylic acid, arachidic acid, heicosyl acid Saturated fatty acids such as behenic acid, tricosylic acid, lignoceric acid, serotic acid, montanic acid, melicic acid, 4-decenoic acid, 4-dodecenoic acid, palmitoleic acid, ⁇ -linolenic acid, linoleic acid, ⁇ -linolenic acid, stearidone Examples thereof include linear unsaturated fatty acids such as acid, petroceric acid, oleic acid, elaidic acid, vaccenic acid, eicosapentaenoic acid, docosapentaenoic acid, do
  • Examples of the metal salts of fatty acids include alkali metals, magnesium, calcium, strontium, barium, titanium, manganese, iron, zinc, silicon, zirconium, yttrium, barium, or hafnium. Particularly, sodium, lithium, potassium, etc.
  • the alkali metal is preferred.
  • the blending amount is preferably 0.001 to 5 parts by weight and more preferably 0.03 to 3.0 parts by weight with respect to 100 parts by weight of the polyolefin resin.
  • antistatic agent examples include cationic antistatic agents such as fatty acid quaternary ammonium ion salts and polyamine quaternary salts; higher alcohol phosphoric acid ester salts, higher alcohol EO adducts, polyethylene glycol fatty acid esters, anionic alkyl sulfones.
  • Anionic antistatic agents such as acid salt, higher alcohol sulfate ester salt, higher alcohol ethylene oxide adduct sulfate ester salt, higher alcohol ethylene oxide adduct phosphate ester salt; polyhydric alcohol fatty acid ester, polyglycol phosphate ester, polyoxyethylene
  • Nonionic antistatic agents such as alkyl allyl ethers
  • amphoteric antistatic agents such as amphoteric alkylbetaines such as alkyldimethylaminoacetic acid betaine and imidazoline type amphoteric activators.
  • Antistatic agents may be used alone, or two or more types of antistatic agents may be used in combination.
  • the blending amount when blending the antistatic agent is preferably 0.01 to 20 parts by mass, more preferably 3 to 10 parts by mass with respect to 100 parts by mass of the polyolefin resin.
  • a commercially available pigment can also be used as the pigment, for example, Pigment Red 1, 2, 3, 9, 10, 17, 22, 23, 31, 38, 41, 48, 49, 88, 90, 97, 112, 119, 122, 123, 144, 149, 166, 168, 169, 170, 171, 177, 179, 180, 184, 185, 192, 200, 202, 209, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 254; Pigment Orange 13, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 65, 71; Pigment Yellow 1, 3, 12, 13, 14, 16, 17, 20, 24, 55, 60, 73, 81, 83, 86, 93, 95, 97, 98, 100 109, 110, 113, 114, 117, 120, 125, 126, 127, 129, 137, 138, 139, 147, 148
  • Dyes include, for example, azo dyes, anthraquinone dyes, indigoid dyes, triarylmethane dyes, xanthene dyes, alizarin dyes, acridine dyes, stilbene dyes, thiazole dyes, naphthol dyes, quinoline dyes, nitro dyes, indamine dyes, oxazine dyes, phthalocyanine Examples thereof include dyes and dyes such as cyanine dyes, and a plurality of these may be used in combination.
  • the method of blending the metal salt of the dicarboxylic acid hydrazide compound with the polyolefin resin is not particularly limited, and can be performed by a conventionally known method.
  • polypolyolefin-based resin powder or pellets and an additive may be mixed by dry blending, and a part of the additive may be preblended and then dry blended with the remaining components.
  • 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 220 ° C.
  • a method of adding an additive at the polymerization stage of a polyolefin-based resin, after mixing in a desired ratio together with a granulating aid such as a binder, wax, solvent, silica, etc., and then granulating to make a one-pack composite additive A method of adding a one-pack composite additive to a polyolefin resin, a method of preparing a masterbatch containing the additive at a high concentration, and adding the masterbatch to the polyolefin resin can be used.
  • the resin composition of the present invention can be obtained by uniformly mixing and kneading the above components.
  • the method is not particularly limited, for example, dry blending is performed with a mixer such as a Henschel mixer or a tumbler, and the processing temperature is 100 ° C. using an extruder, a Banbury mixer, a roll, a Brabender plastograph, a kneader, or the like. Manufactured by kneading at ⁇ 260 ° C.
  • the mixer is manufactured using a Henschel mixer, and the processing machine is manufactured using an extruder, particularly a twin screw extruder.
  • the molded article of the present invention is molded using the resin composition of the present invention. Molding can be performed using a known molding method. For example, a molded product can be obtained using an injection molding method, an extrusion molding method, a blow molding method, a vacuum molding method, an inflation molding method, a calendar molding method, a slush molding method, a dip molding method, a foam molding method, or the like.
  • Applications of the molded article of the present invention include automobile materials such as bumpers, dashboards and instrument panels, housing applications such as refrigerators, washing machines and vacuum cleaners, household goods such as tableware, buckets and bathing goods, miscellaneous goods such as toys, and tanks. Examples of such products include molded products such as storage and storage containers, films, and fibers.
  • Phenolic antioxidant tetrakis [methylene-3- (3 ′, 5′-ditert-butyl-4′-hydroxyphenyl) propionate per 100 parts by mass of homopolypropylene (melt flow rate: 7.7 g / 10 min) ] 0.05 part by weight of methane, phosphorus antioxidant: 0.1 part by weight of tris (2,4-di-tert-butylphenyl) phosphite, metal soap: 0.05 part by weight of calcium stearate, and Table 1 A nucleating agent compound (3-1), (3-2), (3-3), (3-4) in the amount shown in FIG.
  • Example 6 was added and mixed, and a twin screw extruder manufactured by Ikegai Co., Ltd. (with PCM30, 60 mesh) Was granulated at an extrusion temperature of 230 ° C. to obtain pellets.
  • a twin screw extruder manufactured by Ikegai Co., Ltd. (with PCM30, 60 mesh) was granulated at an extrusion temperature of 230 ° C. to obtain pellets.
  • the polyolefin resin compositions (Examples 1 to 7) of the present invention were obtained.
  • a pellet of a composition for comparison (Comparative Example 1) was obtained under the same conditions except that the nucleating agent compound was changed to sodium benzoate.
  • the test piece manufactured by shrinkage ratio anisotropy (4) was immediately placed in a thermostat at 23 ° C. and 50% humidity for 48 hours after molding.
  • the ratio (L MD / L TD ) of the MD direction (resin flow direction) dimension (L MD ) (mm) and the TD direction (width direction) dimension (L TD ) (mm) of the test specimen after standing is a polyolefin resin. It was calculated as an index (shrinkage ratio anisotropy) of a dimensional change of a molded article made of the composition. The closer the shrinkage ratio anisotropy is to 1, the higher the dimensional stability of the molded product shape. The results are shown in Table 1.
  • Examples 1 to 8 a significant increase in the crystallization temperature is seen compared to Comparative Example 1 in which no nucleating agent was added.
  • Sodium benzoate used in Comparative Example 2 is a conventional nucleating agent, and its crystallization temperature raising effect is poor compared to Examples 1-8. Therefore, the nucleating agent compounds (3-1), (3-2), (3-3), and (3-4) have a remarkable effect of improving the crystallization temperature with respect to polyolefin resins, particularly polypropylene resins, That is, it can be seen that it has a remarkable nuclear growth effect.
  • the nucleating agent compound of the present invention impairs the mechanical properties of the polyolefin resin. It can be seen that it exhibits the function as a nucleating agent while improving the mechanical properties of the polyolefin resin. In addition, it can be seen from the results in Table 1 that there is no problem in the dimensional stability of the molded product obtained from the polyolefin resin composition by blending the nucleating agent of the present invention.
  • the compounds of the present invention contribute to the production of molding materials containing polyolefin resins as excellent nucleating agents for polyolefin resins.
  • the polyolefin-based resin composition containing the compound of the present invention as a nucleating agent is particularly suitable for automotive materials, housing materials, mechanical / mechanical parts, and the like.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
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  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Le problème décrit par la présente invention est de fournir un nouvel agent de nucléation à haute performance pour des résines de polyoléfine. La solution selon l'invention concerne un composé représenté par la formule générale (1) ; un agent de nucléation comprenant le composé ; une composition de résine de polyoléfine contenant l'agent de nucléation ; et un article moulé formé à partir de la composition de résine de polyoléfine. (Dans la formule (1), l'anneau A et l'anneau B représentent indépendamment un groupe aryle ou un groupe cycloalkyle ; et M représente un atome de métal alcalin.)
PCT/JP2017/047339 2017-02-16 2017-12-28 Nouveau composé, agent de nucléation, composition de résine et article moulé WO2018150755A1 (fr)

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