Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J3/00—Processes of treating or compounding macromolecular substances
  • C08J3/20—Compounding polymers with additives, e.g. colouring
  • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/18—Manufacture of films or sheets
• • 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
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
  • C08K3/20—Oxides; Hydroxides
  • C08K3/22—Oxides; Hydroxides of metals
• • 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
  • C08K5/04—Oxygen-containing compounds
  • C08K5/10—Esters; Ether-esters
  • C08K5/101—Esters; Ether-esters of monocarboxylic acids
  • C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols
• • 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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
  • C08L91/06—Waxes
• • D—TEXTILES; PAPER
  • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
  • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
  • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
  • D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
  • D01F6/46—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polyolefins

Definitions

• the present invention relates to a thermoplastic resin composition and a method for producing a thermoplastic resin composition.
• Metal oxides are used for various purposes due to their high activity. However, when a metal oxide is used as a polymer composite material, it is known that it is difficult to disperse the metal oxide because of its high cohesiveness.
• pellet-shaped, flake-shaped, or bead-shaped master batches in which oxides are dispersed are used properly depending on the intended use, taking advantage of their characteristics.
• the masterbatch is preferably used from the viewpoint of ease of handling and preservation of the working environment at the time of use.
• stearic acid zinc stearate, magnesium stearate, aluminum stearate, calcium stearate, ethylene bisamide, polyethylene wax, polypropylene wax, and One or more of these derivatives, such as waxes made of acid-modified products, are used.
• a high-speed pigment dispersion such as spinning a thermoplastic resin at a diameter of 20 ⁇ m or less at high speed or forming a film
• the above dispersant may not be satisfied. That is, yarn breakage during spinning due to poor dispersion, clogging of the filter of the melt spinning machine, molding failure in the film, and the like occur.
• efforts have been made to improve the dispersibility by improving the processing method of the masterbatch and using a powerful kneader, but the dispersibility has not been sufficiently exhibited.
• a method for producing a colored resin composition comprising the step (D) of removing a solvent and water from the mixture after flushing obtained in C) has been proposed (Patent Document 2).
• C n H 2n + 1 (OCH 2 CH 2 ) m OH ... (1) In the equation, n is an integer from 1 to 100, and m is an integer from 1 to 100.
• the pigment-containing aqueous slurry and the heat-meltable resin are mixed to prepare a mixture of water, the pigment and the heat-meltable resin, and the mixture is dehydrated so that the water content in the mixture is 4 to 25% by mass.
• the mixture was continuously charged into an extrusion kneader having at least one vent port and kneaded at a temperature equal to or higher than the melting temperature of the heat-meltable resin, so that the separated water content and the remaining water content were separated.
• Patent Document 3 A method for producing a resin composition has been proposed (Patent Document 3).
• An object of the present invention is to provide a thermoplastic resin composition and a method for producing a thermoplastic resin composition, which can realize high dispersion of an inorganic compound and improve the processability, mechanical properties, and appearance quality of a molded product. There is something in it.
• the inventors have conducted diligent research to produce a masterbatch using an aqueous dispersion containing amphoteric molecules, and the obtained masterbatch and a predetermined amount of oxide wax.
• a thermoplastic resin composition or a thermoplastic resin molded product By mixing with the base resin to which the above-mentioned material is added to obtain a thermoplastic resin composition or a thermoplastic resin molded product, while suppressing deterioration of the polyolefin resin, aggregation of the inorganic compound in the aqueous dispersion as an inorganic compound slurry
• the inorganic compound was highly dispersed in the masterbatch, and the processability, mechanical properties, and appearance quality of the thermoplastic resin molded product could be improved.
• the present invention provides the following means.
• Polyolefin resin (A) and Inorganic compounds mainly composed of metal oxides and With amphipathic molecules, Oxidized wax and Contains When the total mass of the polyolefin resin (A), the inorganic compound, the amphipathic molecule, and the oxide wax in the masterbatch is 100% by mass, the content of the oxide wax is 0.01% by mass or more. Masterbatch that is 25% by weight or less.
• the content of the amphipathic molecule is 0 when the total mass of the polyolefin resin (A), the inorganic compound, the amphipathic molecule and the oxide wax in the masterbatch is 100% by mass.
• the amphoteric molecule is selected from glycerin fatty acid ester, polyglycerin fatty acid ester, propylene glycol fatty acid ester, sorbitan fatty acid ester, polyoxyethylene alkyl ether, polyoxyethylene alkylamine, and polyoxyethylene alkylamide 1.
• amphipathic molecule comprises one or more selected from sorbitan fatty acid ester and polyoxyethylene alkyl ether.
• polyolefin resin (A) comprises one or two selected from polypropylene, high-density polyethylene, low-density polyethylene and polymethylpentene.
• thermoplastic resin composition comprising the masterbatch according to any one of the above [1] to [5] and the polyolefin resin (B).
• thermoplastic resin composition When the total mass of the masterbatch and the polyolefin resin (B) in the thermoplastic resin composition is 100% by mass, the content of the masterbatch is 1% by mass or more and 90% by mass or less.
• thermoplastic resin molded product obtained by melt-molding the thermoplastic resin composition according to any one of the above [6] to [8].
• thermoplastic resin molded product obtained by blending the masterbatch according to any one of the above [1] to [5] with the polyolefin resin (B).
• thermoplastic resin molded product When the total mass of the masterbatch and the polyolefin resin (B) in the thermoplastic resin molded product is 100% by mass, the content of the masterbatch is 1% by mass or more and 90% by mass or less.
• thermoplastic resin molded product according to any one of [9] to [12] above, wherein the thermoplastic resin molded product is selected from filaments, staples, non-woven fabrics, hollow threads, and films.
• a method of manufacturing a masterbatch A method of manufacturing a masterbatch.
• thermoplastic resin composition which comprises a step of melt-mixing the masterbatch obtained by the production method according to the above [14] and the polyolefin resin (B).
• the content of the masterbatch is 1% by mass or more and 90% by mass or less when the total mass of the masterbatch and the polyolefin resin (B) is 100% by mass.
• thermoplastic resin molded product which comprises a step of melt-molding the thermoplastic resin composition obtained by the production method according to the above [15] or [16].
• thermoplastic resin molded product which comprises a step of melt-mixing the masterbatch obtained by the production method according to the above [14] and the polyolefin resin (B).
• the content of the masterbatch is 1% by mass or more and 90% by mass or less when the total mass of the masterbatch and the polyolefin resin (B) is 100% by mass.
• the present invention it is possible to realize high dispersion of the inorganic compound and improve the processability, mechanical properties, and appearance quality of the molded product.
• the masterbatch (also referred to as a thermoplastic resin composition) of the present embodiment includes a polyolefin resin (A), an inorganic compound containing a metal oxide as a main component, an amphoteric molecule, and a polyolefin resin (A) in the masterbatch. ),
• the oxide wax having a content of 0.01% by mass or more and 25% by mass or less when the total mass of the inorganic compound, the amphoteric molecule and the oxide wax is 100% by mass is contained.
• the content of the polyolefin resin (A) is preferably 30% by mass or more. , More preferably 40% by mass or more, further preferably 50% by mass or more, and preferably 99% by mass or less.
• the content of the polyolefin resin (A) is 30% by mass or more, the content of the polyolefin resin (A) as a matrix resin with respect to the inorganic compound becomes an appropriate amount, and the inorganic compound can be more easily dispersed in the master batch.
• it is 99% by mass or less the amount of the inorganic compound becomes appropriate, and it becomes easier to express the desired characteristics of the inorganic compound. Therefore, the content of the polyolefin resin (A) is set to a value within the above range.
• the polyolefin-based resin is a polyolefin resin obtained by polymerizing at least one kind of olefin, and may be a homopolymer or a copolymer.
• olefins include ⁇ -olefins having 4 to 12 carbon atoms including ethylene, propylene, isobutylene, and isobutene (1-butene), butadiene, isoprene, (meth) acrylic acid ester, and (meth) acrylic acid. , (Meta) acrylamide, vinyl alcohol, vinyl acetate, vinyl chloride, styrene, acrylonitrile and the like.
• Examples of ⁇ -olefins having 4 to 12 carbon atoms include 1-butene, 2-methyl-1-propene, 2-methyl-1-butene, 3-methyl-1-butene, 1-hexene, and 2 -Ethyl-1-butene, 2,3-dimethyl-1-butene, 2-methyl-1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 3,3-dimethyl-1-butene , 1-hexene, methyl-1-hexene, dimethyl-1-pentene, ethyl-1-pentene, trimethyl-1-butene, methylethyl-1-butene, 1-octene, methyl-1-pentene, ethyl-1- Hexene, dimethyl-1-hexene, propyl-1-heptene, methylethyl-1-heptene, trimethyl-1-pentene, propyl-1-pentene, diethyl-1-buten
• the polyolefin resin is not particularly limited, and examples thereof include polyethylene resin, polypropylene resin, polymethylpentene resin, polyisobutylene resin, polyisobutene resin, polyisoprene resin, and polybutadiene resin. Of these resins, polyethylene resin, polypropylene resin, and polymethylpentene resin are preferable.
• high-density polyethylene When classified by density or shape, high-density polyethylene (HDPE), low-density polyethylene (LDPE), ultra-low-density polyethylene (VLDPE), linear low-density polyethylene (LLDPE), and ultra-high molecular weight polyethylene (UHMW-PE) are available. Of these, high-density polyethylene and low-density polyethylene (LDPE) are preferable.
• thermoplastic resin (A) is preferably made of one or more selected from polypropylene, high-density polyethylene, low-density polyethylene and polymethylpentene from the viewpoint of molding into threads and films.
• the inorganic compound contains a metal oxide as a main component.
• the main component means that the metal oxide is larger than 50% by mass when the total mass of the inorganic compound is 100% by mass.
• the inorganic compound may be composed of one kind or two or more kinds of metal oxides.
• the content of the inorganic compound is preferably in the range of 1% by mass or more. It is good, preferably 70% by mass or less, more preferably 60% by mass or less, still more preferably 50% by mass or less.
• the content of the inorganic compound is 1% by mass or more, the desired characteristics of the inorganic compound are easily exhibited, and when it is 70% by mass or less, the inorganic compound is easily uniformly dispersed in the masterbatch.
• the metal compound is not particularly limited, and is, for example, titanium (Ti), silicon (Si), zinc (Zn), aluminum (Al), copper (Cu), iron (Fe), molybdenum (Mo), and zirconia (Zr). ) And other metal oxides. Further, one selected from these inorganic compounds may be used alone, or two or more thereof may be used in combination. Further, it may be a solid solution of the above metal, an inorganic substance stable to water, or the like.
• amphipathic molecule examples include the following compounds.
• Glycerin fatty acid esters such as glyceryl monostearate (HLB value 4.0), self-emulsifying glyceryl monostearate (HLB value 6.0), glyceryl monooleate (HLB value 2.5); -Polyglyceryl-6 (HLB value 3.9), diglyceryl monostearate (HLB value 5.0), diglyceryl monooleate (HLB value 6.5), diglyceryl dioleate (HLB value 7.).
• HLB value 4.0 glyceryl monostearate
• HLB value 6.0 self-emulsifying glyceryl monostearate
• HLB value 2.5 glyceryl monooleate
• -Polyglyceryl-6 HLB value 3.9
• diglyceryl monostearate HLB value 5.0
• diglyceryl monooleate HLB value 6.5
• diglyceryl dioleate HLB value 7.
• Decaglyceryl monostearate (HLB value 12.0), decaglyceryl monoisostearate (HLB value 12.0), decaglyceryl monooleate (HLB value 12.0), decaglyceryl diisostearate (HLB value 10.0) )
• HLB value 12.0 decaglyceryl monostearate
• HLB value 12.0 decaglyceryl monooleate
• HLB value 10.0 decaglyceryl diisostearate
• B Polyglycerin fatty acid esters
• -Propylene glycol monolaurate (HLB value 4.2), propylene glycol monopalmitate (HLB value 3.8), propylene glycol monostearate (HLB value 3.7), propylene glycol monooleate (HLB value 3.6).
• Propylene glycol fatty acid esters such as propylene glycol monobehenate (HLB value 3.4); -Sorbitan monopalmitate (HLB value 6.7), sorbitan monostearate (HLB value 4.7), sorbitan sesquistearate (HLB value 4.2), sorbitan tristearate (HLB value 2.1), mono.
• Polysorbate fatty acids such as sorbitan isostearate (HLB value 5.0), sorbitan sesquiisostearate (HLB value 4.5), sorbitan monooleate (HLB value 4.3), sorbitan sesquioleate (HLB value 3.7).
• amphipathic molecules may be used alone, or two or more thereof may be used in combination.
• the content of the amphipathic molecule is preferably 0.01% by mass.
• the above range may be used, preferably 40% by mass or less, more preferably 30% by mass or less, and further preferably 20% by mass or less.
• the content of amphipathic molecules is 0.01% by mass or more and 40% by mass or less, the thermal stability of the masterbatch during melt mixing is further improved, and the dispersion of the inorganic compound in the polyolefin resin (A) is dispersed. It can be more stable.
• the mass ratio of the amphipathic molecule (A) to the amphipathic molecule (B) in the master batch is the amphipathic molecule.
• the sex molecule (A): amphipathic molecule (B) 10 to 90: 90 to 10, and more preferably 20 to 80: 80 to 20.
• the content of the oxide wax is 0.01% by mass as described above. It may be in the range of 25% by mass or more, preferably 0.1% by mass or more, more preferably 1% by mass or more, and preferably 25% by mass or less.
• the content of the oxide wax is 0.01% by mass or more and 25% by mass or less, the dispersion of the inorganic compound in the polyolefin resin (A) can be made more stable, and the resin processing of the fiber is particularly stable during processing. At times, flexibility and heat resistance can be imparted, and high-speed sewing and tensile strength can be improved.
• the oxide wax is, for example, a polyolefin wax obtained by polymerizing at least one kind of olefin, and may be a homopolymer or a copolymer.
• the polyolefin wax is, for example, polyethylene wax or polypropylene wax.
• the molecular weight of the oxidized wax may be preferably in the range of 100 or more, more preferably 500 or more, still more preferably 1000 or more, and preferably in the range of 50,000 or less, more preferably 30,000 or less, still more preferably 15,000 or less.
• the density of the oxide wax may be preferably in the range of 700 kg / m 3 or more, more preferably 750 kg / m 3 or more, further preferably 800 kg / m 3 or more, and preferably 1300 kg / m 3 or less, more preferably 1200 kg. It may be in the range of / m 3 or less, more preferably 1100 kg / m 3 or less.
• the acid value of the oxidized wax may be preferably in the range of 1 mgKOH / g or more, more preferably 3 mgKOH / g or more, still more preferably 5 mgKOH / g or more, and preferably 300 mgKOH / g or less, more preferably 200 mgKOH / g or less. , More preferably, it may be in the range of 100 mgKOH / g or less.
• one kind selected from these oxide waxes may be used alone, or two or more kinds may be used in combination.
• the masterbatch may contain other components other than the polyolefin resin (A), the inorganic compound, the amphipathic molecule and the oxide wax as long as the purpose of the function is not deviated.
• specific examples of other components include antioxidants, ultraviolet absorbers, colorants, pigments, dyes, foaming agents, lubricants, flame retardants, fillers and the like.
• thermoplastic resin composition and the molded product of the present embodiment are made by blending a masterbatch and a polyolefin resin (B).
• the thermoplastic resin composition or molded product is a cured product of a mixture of the masterbatch and the polyolefin resin (B) (a state of being softened and fluidized by heating and solidified by cooling).
• the thermoplastic resin composition is not particularly limited, but is, for example, an intermediate molded product for obtaining a thermoplastic resin molded product from a masterbatch, and means a material having a predetermined form such as pellets or powder.
• the content of the masterbatch may be preferably in the range of 1% by mass or more. Further, it may be preferably in the range of 90% by mass or less, more preferably 80% by mass or less, and further preferably 70% by mass or less.
• the polyolefin-based resin is a polyolefin resin obtained by polymerizing at least one kind of olefin, and may be a homopolymer or a copolymer.
• olefins include ⁇ -olefins having 4 to 12 carbon atoms including ethylene, propylene, isobutylene, and isobutene (1-butene), butadiene, isoprene, (meth) acrylic acid ester, and (meth) acrylic acid. , (Meta) acrylamide, vinyl alcohol, vinyl acetate, vinyl chloride, styrene, acrylonitrile and the like.
• Examples of ⁇ -olefins having 4 to 12 carbon atoms include 1-butene, 2-methyl-1-propene, 2-methyl-1-butene, 3-methyl-1-butene, 1-hexene, and 2 -Ethyl-1-butene, 2,3-dimethyl-1-butene, 2-methyl-1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 3,3-dimethyl-1-butene , 1-hexene, methyl-1-hexene, dimethyl-1-pentene, ethyl-1-pentene, trimethyl-1-butene, methylethyl-1-butene, 1-octene, methyl-1-pentene, ethyl-1- Hexene, dimethyl-1-hexene, propyl-1-heptene, methylethyl-1-heptene, trimethyl-1-pentene, propyl-1-pentene, diethyl-1-buten
• the polyolefin resin is not particularly limited, and examples thereof include polyethylene resin, polypropylene resin, polymethylpentene resin, polyisobutylene resin, polyisobutene resin, polyisoprene resin, and polybutadiene resin. Of these resins, polyethylene resin, polypropylene resin, and polymethylpentene resin are preferable.
• high-density polyethylene When classified by density or shape, high-density polyethylene (HDPE), low-density polyethylene (LDPE), ultra-low-density polyethylene (VLDPE), linear low-density polyethylene (LLDPE), and ultra-high molecular weight polyethylene (UHMW-PE) are available. Of these, high-density polyethylene and low-density polyethylene (LDPE) are preferable.
• thermoplastic resin (A) is preferably made of one or more selected from polypropylene, high-density polyethylene, low-density polyethylene and polymethylpentene from the viewpoint of molding into threads and films.
• the polyolefin resin (B) in the thermoplastic resin composition or the molded product may be the same type as or different from the polyolefin resin (A), but the same type of resin should be used from the viewpoint of compatibility. Is preferable.
• the content of the amphoteric molecules is preferably in the range of 0.01% by mass or more. It is good, preferably 40% by mass or less, more preferably 30% by mass or less, still more preferably 20% by mass or less.
• amphipathic molecules of different types (for example, HLB)
• amphipathic molecule (A) and the amphipathic molecule (B) in the thermoplastic resin composition or the molded product are used.
• amphipathic molecule (A): amphipathic molecule (B) 10 to 90: 90 to 10, and more preferably 20 to 80: 80 to 20.
• the content of the oxide wax is preferably 0.01% by mass or more, more preferably. It may be in the range of 0.1% by mass or more, more preferably 1% by mass or more, and more preferably 25% by mass or less.
• thermoplastic resin composition or molded product is other than the polyolefin resin (A), the inorganic compound, the amphipathic molecule (A), the oxide wax and the amphipathic molecule (B), as long as the purpose of the function is not deviated.
• Other ingredients may be included. Specific examples of other components include antioxidants, ultraviolet absorbers, colorants, pigments, dyes, foaming agents, lubricants, flame retardants, fillers and the like.
• the form of the thermoplastic resin molded product is not limited, but may be selected from, for example, filaments (long fibers), staples (short fibers), non-woven fabrics, and hollow fibers.
• the filament may be a multifilament in which several tens of single yarns (single fibers) are twisted together, or may be a monofilament having one single yarn.
• the thermoplastic resin molded product may be a film.
• the method for producing a master batch according to the present embodiment is an aqueous dispersion in which an inorganic compound containing a metal oxide as a main component and an amphoteric molecule are mixed and the above inorganic compound is contained in an amount of 1% by mass or more and 80% by mass or less.
• the content of the oxide wax is 0.01% by mass or more and 20% by mass or less.
• the aqueous dispersion is supplied in an amount of 1 part by mass or more and 300 parts by mass or less, and has a step (II) of melt-mixing.
• the content of the inorganic compound is 1% by mass or more and 80% by mass or less. It may be preferably in the range of 1% by mass or more and 70% by mass or less, and more preferably 1% by mass or more and 60% by mass or less. If the content of the inorganic compound is less than 1% by mass, it becomes difficult to obtain the desired properties of the inorganic compound in the thermoplastic resin composition or the molded product, and if it is more than 80% by mass, it becomes difficult to obtain high dispersion of the inorganic compound. , Deterioration of mechanical properties and poor appearance are likely to occur. Therefore, the content of the inorganic compound in the aqueous dispersion is set to a value within the above range.
• the content of the amphipathic molecule may be preferably in the range of 0.01% by mass or more. Further, it may be preferably in the range of 40% by mass or less, more preferably 30% by mass or less, and further preferably 20% by mass or less.
• the content of the amphipathic molecular agent is 0.01% by mass or more and 40% by mass or less, the inorganic compound can be more compatible with the polyolefin resin (A).
• the content of the oxide wax is 0.01% by mass or more and 20% by mass or less as described above. It may be in the range of 0.1% by mass or more, more preferably 1% by mass or more, and preferably 20% by mass or less.
• the content of the polyolefin resin (A) may be preferably in the range of 80% by mass or more, and also. It may be preferably in the range of 99% by mass or less, more preferably 97% by mass or less, and further preferably 95% by mass or less.
• an aqueous dispersion may be prepared by further mixing a water-soluble alcohol with an inorganic compound containing a metal oxide as a main component and an amphipathic molecule.
• the content of the inorganic compound is preferably 100% by mass when the total mass of the inorganic compound, the amphoteric molecule, the water-soluble alcohol and water in the aqueous dispersion used in the step (I) is 100% by mass.
• the content of the inorganic compound is less than 1% by mass, it becomes difficult to obtain the desired properties of the inorganic compound in the thermoplastic resin composition or the molded product, and if it is more than 80% by mass, it becomes difficult to obtain high dispersion of the inorganic compound. , Deterioration of mechanical properties and poor appearance are likely to occur. Therefore, the content of the inorganic compound in the aqueous dispersion is set to a value within the above range.
• the content of the amphipathic molecule is preferably 0.01% by mass or more.
• the range may be preferably 40% by mass or less, more preferably 30% by mass or less, still more preferably 20% by mass or less.
• the inorganic compound can be more compatible with the polyolefin resin (A).
• the content of the water-soluble alcohol is preferably in the range of 0.01% by mass or more. It may be in the range of 40% by mass or less, more preferably 30% by mass or less, and further preferably 20% by mass or less.
• the content of the water-soluble alcohol is 0.01% by mass or more and 40% by mass or less, the stability of the system can be improved.
• the aqueous dispersion may contain other components other than the above-mentioned inorganic compound, amphipathic molecule and water-soluble alcohol as long as the purpose of the function is not deviated.
• specific examples of other components include antioxidants, ultraviolet absorbers, colorants, pigments, dyes, foaming agents, lubricants, flame retardants, fillers and the like.
• the mixture is adjusted so that the content of the oxide wax is 0.01% by mass or more and 20% by mass or less when the total mass of the polyolefin resin (A) and the oxide wax is 100% by mass.
• (A) is obtained, and then the aqueous dispersion prepared in the step (I) is supplied in an amount of 1 part by mass or more and 300 parts by mass or less with respect to 100 parts by mass of the mixture (A), and melt-mixed to master. Get a batch.
• the amount of the aqueous dispersion supplied to the mixture (A) may be preferably in the range of 1 part by mass or more and 200 parts by mass or less.
• the supply amount of the aqueous dispersion is larger than 300 parts by mass, it is difficult to inject it into the apparatus for melting and mixing, and it is difficult to raise the temperature to the melting temperature of the polyolefin resin (A), which makes melting and mixing difficult.
• the supply amount of the aqueous dispersion with respect to the polyolefin resin (A) is 1 part by mass or more and 300 parts by mass or less, secondary aggregation of the inorganic compound is prevented during dehydration drying of the melt mixture, and metal oxidation in the master batch. Objects can be uniformly dispersed. Therefore, the supply amount of the aqueous dispersion is set to a value within the above range.
• the content of the mixture (A) when the total mass of the mixture (A) and the aqueous dispersion in the mixture (B) is 100% by mass.
• the ratio may be preferably in the range of 25% by mass or more, more preferably 35% by mass or more, further preferably 40% by mass or more, and preferably 99% by mass or less.
• the content of the aqueous dispersion may be preferably in the range of 1% by mass or more, and also.
• the range may be preferably 75% by mass or less, more preferably 65% by mass or less, still more preferably 60% by mass or less.
• a kneader such as an extruder (single-screw extruder, twin-screw extruder), kneader, or Banbury mixer can be used.
• the kneading extruder is capable of continuous kneading. Is preferable.
• the heating temperature in the melting and mixing step is determined according to the ease of melting of the polyolefin resin as the matrix resin, but is preferably in the range of 120 ° C. or higher, more preferably 130 ° C. or higher, and further preferably 140 ° C. or higher. It may be well, preferably 240 ° C. or lower, more preferably 230 ° C.
• the heating temperature is 120 ° C. or higher, the polyolefin resin is easily melted, and the inorganic compound is easily dispersed in the polyolefin resin.
• the heating temperature is 240 ° C. or lower, thermal deterioration of each component can be suppressed.
• an aqueous dispersion containing a water-soluble alcohol may be used.
• the aqueous dispersion prepared in the step (I) is preferably 1 part by mass or more and 300 parts by mass or less, more preferably 1 part by mass or more and 200 parts by mass or less, based on 100 parts by mass of the mixture (A). More preferably, it may be supplied in an amount of 1 part by mass or more and 150 parts by mass or less and melt-mixed.
• the content of the mixture (A) when the total mass of the mixture (A) and the aqueous dispersion in the mixture (B) is 100% by mass.
• the ratio may be preferably in the range of 25% by mass or more, more preferably 35% by mass or more, further preferably 40% by mass or more, and preferably 99% by mass or less.
• the content of the aqueous dispersion is preferably in the range of 1% by mass or more when the total mass of the mixture (A) and the aqueous dispersion in the mixture (B) is 100% by mass. It may be in the range of preferably 75% by mass or less, more preferably 65% by mass or less, still more preferably 60% by mass or less.
• the masterbatch After melt-mixing, the masterbatch can be molded or processed into a shape (for example, pellet form) according to the purpose of use.
• a shape for example, pellet form
• the pellet-shaped masterbatch can be used as a material for further molding, for example, as a material for a thermoplastic resin composition or a molded product.
• the pellet-shaped masterbatch can be molded by a molding machine (for example, an injection molding machine, an extrusion molding machine, etc.).
• thermoplastic resin composition and molded product In the method for producing a thermoplastic resin composition or a molded product according to the present embodiment, the masterbatch obtained by the above production method and the polyolefin resin (B) are melt-mixed. Thereby, the above-mentioned thermoplastic resin molded product can be directly obtained, but once the step of obtaining the pellet-shaped or powder-shaped thermoplastic resin composition is performed, the obtained pellet-shaped or powder-shaped thermoplastic resin is obtained. It is also possible to obtain a desired thermoplastic resin molded product through a step of melt-molding the composition.
• thermoplastic resin molded product By obtaining the thermoplastic resin molded product via the master batch in this way, the inorganic compound can be stably and uniformly dispersed in the thermoplastic resin molded product, and the desired function and characteristics of the inorganic compound can be obtained thermoplastically. It can be sufficiently applied to the resin molded body. Further, by molding the thermoplastic resin molded product through the masterbatch, hydrolysis of the polyolefin resin is significantly suppressed, and moldability (processability), mechanical properties and appearance quality can be improved.
• the content of the masterbatch is preferably 1% by mass or more and 90% by mass or less, more preferably 1% by mass or more and 80% by mass.
• the content of the masterbatch is 1% by mass or more and 90% by mass or less, the inorganic compound can be more stably and uniformly dispersed.
• components other than the masterbatch and the polyolefin resin (B) may be further mixed.
• the antioxidant can be mixed with the masterbatch and the polyolefin resin (B).
• the thermoplastic resin molded product can be molded or processed into a shape (for example, thread-like, non-woven fabric-like, film-like) according to the purpose of use.
• a shape for example, thread-like, non-woven fabric-like, film-like
• the thermoplastic resin molded body is in the form of threads (filaments, staples, hollow threads)
• the molten resin can be discharged from one or a plurality of holes having a predetermined cross-sectional shape to form a thread.
• the filamentous thermoplastic resin molded product may be further subjected to post-treatment such as stretching, heat treatment, and twisting, or may be mixed with other yarns and spun to form a blended yarn or a blended yarn. good.
• thermoplastic resin molded body When the thermoplastic resin molded body is made into a nonwoven fabric, it can be made into a nonwoven fabric by accumulating fibers formed from the molten resin on a net after melt-kneading.
• the non-woven fabric-like thermoplastic resin molded product may be further subjected to post-treatment such as binding the fibers with each other by a binder or entwining the fibers with each other by applying an external force.
• the thermoplastic resin molded product When the thermoplastic resin molded product is in the form of a film, it can be formed into a film by being melt-kneaded and then ejected (extruded) from the molten resin through a slit-shaped hole.
• the film-shaped thermoplastic resin molded product may be further molded by a press molding method or a vacuum forming method, or may be formed on a base layer to form a multilayer film.
• Example 1 Manufacturing of aqueous dispersion
• Titanium oxide particles (“ST-21” manufactured by Ishihara Sangyo Co., Ltd., average particle diameter 20 nm) 30 parts by mass, polyoxyethylene alkyl ether as amphipathic molecule (“Safety Cut LI-3085” manufactured by Aoki Oil & Fat Co., Ltd., HLB value) 13.9)
• 68 parts by mass of water was added to 1 part by mass of 1 part by mass and 1 part by mass of ethanol as a water-soluble alcohol, and an aqueous dispersion (1) was obtained using a homogenizer.
• Example 2 Manufacturing of aqueous dispersion
• amphipathic molecule was changed to a sorbitan fatty acid ester (“Ionet S-80” manufactured by Sanyo Chemical Industries, Ltd., HLB value 4.3) to obtain an aqueous dispersion (2). rice field.
• a master batch (2) was obtained in the same manner as in Example 1 except that the aqueous dispersion (1) was changed to the aqueous dispersion (2).
• Example 3 Manufacturing of aqueous dispersion
• Amphiphile molecules are polyoxyethylene alkyl ether (“Safety Cut LI-3085” manufactured by Aoki Oil & Fat Co., Ltd., HLB value 13.9) and sorbitan fatty acid ester (“Ionet S-80” manufactured by Sanyo Kasei Kogyo Co., Ltd., HLB value.
• the same procedure as in Example 1 was carried out except that the two types were changed to 4.3) to obtain an aqueous dispersion (3).
• a masterbatch (3) was obtained in the same manner as in Example 1 except that the aqueous dispersion (1) was changed to the aqueous dispersion (3).
• Example 4 Manufacturing of masterbatch
• a masterbatch (4) was obtained in the same manner as in Example 1 except that the oxide wax was changed to 5 parts by mass.
• Example 2 Manufacturing of filament The same procedure as in Example 1 was carried out except that the masterbatch (1) was changed to the masterbatch (4) to obtain a filament (4).
• Example 5 (Manufacturing of masterbatch) A masterbatch (5) was obtained in the same manner as in Example 1 except that the oxide wax was changed to 20 parts by mass.
• Example 2 Manufacturing of filament The same procedure as in Example 1 was carried out except that the masterbatch (1) was changed to the masterbatch (5), to obtain a filament (5).
• Example 6 Manufacturing of aqueous dispersion
• the titanium oxide particles were changed to silicon oxide particles (“QSG-30” manufactured by Shin-Etsu Chemical Co., Ltd., average particle diameter 30 nm) to obtain an aqueous dispersion (4).
• a master batch (6) was obtained in the same manner as in Example 1 except that the aqueous dispersion (1) was changed to the aqueous dispersion (4).
• Example 7 Manufacturing of aqueous dispersion
• the same procedure as in Example 1 was carried out except that the titanium oxide particles were changed to zinc oxide particles (“FINEX-30” manufactured by Sakai Chemical Industry Co., Ltd., average particle diameter 35 nm) to obtain an aqueous dispersion (5).
• a master batch (7) was obtained in the same manner as in Example 1 except that the aqueous dispersion (1) was changed to the aqueous dispersion (5).
• Example 8 Manufacturing of masterbatch
• polypropylene was changed to low density polyethylene (“Petrosen (registered trademark) 203” manufactured by Tosoh Corporation) and the extrusion temperature was further changed to 150 ° C., and the masterbatch (8) was carried out. Obtained.
• Example 9 (Manufacturing of masterbatch) Polypropylene was changed to high-density polyethylene (“Suntech HD J320” manufactured by Asahi Kasei Corporation), and the extrusion processing temperature was changed to 150 ° C. in the same manner as in Example 1 to obtain a masterbatch (9).
• Example 10 Manufacturing of masterbatch
• polypropylene was changed to poly-4-methyl-1-pentene (“TPX DX818” manufactured by Mitsui Chemicals, Inc.) and the extrusion temperature was further changed to 280 ° C. 10) was obtained.
• TPX DX818 poly-4-methyl-1-pentene
• Example 11 Manufacturing of film
• 90 parts by mass of polypropylene (“Y-2000GV” manufactured by Prime Polymer Co., Ltd.) is mixed with 10 parts by mass of masterbatch (3), and a film forming temperature of 230 ° C. is used using a 20 mm single-screw extruder connected to a 100 mm wide T-die.
• a film (1) having a thickness of 10 ⁇ m was obtained.
• Example 1 Manufacturing of aqueous dispersion, masterbatch and filament
• polyoxyethylene alkyl ether as an amphipathic molecule was not used to obtain an aqueous dispersion (6), a masterbatch (11) and a filament (12).
• Example 2 Manufacturing of masterbatch and filament
• the oxide wax was changed to 30 parts by mass to obtain a master batch (12) and a filament (12).
• the obtained filaments (1) to (14) were evaluated for the frequency of yarn breakage during spinning. This was carried out 5 times for the same sample and used as an average value. The case where the yarn breakage occurred less than 3 times was regarded as good " ⁇ ", the case of 3 times or more and less than 10 times was regarded as a slightly defective " ⁇ ", and the case of 10 times or more was regarded as a defective "x".
• aqueous dispersions (3) to (5) containing two types of polyoxyethylene alkyl ether and sorbitan fatty acid ester are used as amphipathic molecules, and the polyolefin resin (A) is used.
• polypropylene is used as the polyolefin resin (B)
• the differential pressure of the masterbatch is 1 MPa or less
• the secondary aggregation of the metal oxide is sufficiently prevented in the masterbatch
• the dispersion stability of the metal oxide is extremely high. It turned out.
• master batches (1) to (10) are produced using any of the aqueous dispersions (1) to (5), and filaments (1) to filaments (1) to using the master batch.
• the occurrence of yarn breakage was less than 3 times, and the spinnability of the filament was good.
• master batches (1) to (10) are produced using any of the aqueous dispersions (1) to (5), and filaments (1) to filaments (1) to using the master batch.
• the number of particles having a particle diameter of 20 ⁇ m or more in the filament was 5 or less, secondary aggregation of the metal oxide was prevented during filament molding, and the dispersion stability of the metal oxide was high. ..
• Examples 1 to 8 when either polypropylene or low-density polyethylene is used as the polyolefin resin (A) and the polyolefin resin (B), the number of particles having a particle diameter of 20 ⁇ m or more in the filament is less than one. It was found that the secondary aggregation of the metal oxide was sufficiently prevented during filament molding, and the dispersion stability of the metal oxide was extremely high.
• Example 11 when the masterbatch (3) is manufactured using the aqueous dispersion (3) and the film (1) is manufactured using the masterbatch, the film formation is completed without pressurization, and the film production is completed. The film property was good. Further, in Example 11, when the masterbatch (3) is manufactured using the aqueous dispersion (3) and the film (1) is manufactured using the masterbatch, 1 to 5 particles having a particle diameter of 20 ⁇ m or more are produced. It was found that the secondary aggregation of the metal oxide was prevented during film molding, and the dispersion stability of the metal oxide was high.
• Comparative Example 1 when the master batch (11) was manufactured using the aqueous dispersion (6) and the filament (11) was manufactured using the master batch, yarn breakage occurred 3 times or more and less than 10 times. The spinnability of the filament was slightly poor. Further, in Comparative Example 1, when the masterbatch (11) is manufactured using the aqueous dispersion (6) and the filament (11) is manufactured using the masterbatch, particles having a particle diameter of 20 ⁇ m or more in the filament are produced. The number was 20 or more, and a large number of agglomerated particles were present in the filament as compared with Examples 1 to 11, and the agglomeration prevention property of the metal oxide was inferior.
• Comparative Example 2 it was obtained by adjusting the content of polyethylene wax to be 30% by mass when the total mass of polypropylene as the polyolefin resin (A) and polyethylene wax as the oxide wax was 100% by mass.
• the masterbatch (12) is produced by supplying 30% by mass of the aqueous dispersion with respect to 100% by mass of the mixture (B) of the mixture (A) and the aqueous dispersion, the masterbatch is sintered. It did not pass through the filter, and a large number of aggregated particles were present in the masterbatch, and the antiaggregation property of the metal oxide was inferior.
• Comparative Example 2 when the masterbatch (12) was manufactured and the filament (12) was manufactured using the masterbatch, the yarn breakage occurred 3 times or more and less than 10 times, and the spinnability of the filament was slightly improved. It was bad. Further, in Comparative Example 2, when the masterbatch (12) was manufactured and the filament (12) was manufactured using the masterbatch, 20 or more particles having a particle diameter of 20 ⁇ m or more in the filament were found in Example 1. A large number of agglomerated particles were present in the filament as compared with 10 to 10, and the agglomeration prevention property of the metal oxide was inferior.
• Comparative Example 3 when a master batch (13) containing both polyoxyethylene alkyl ether and sorbitan fatty acid ester as amphipathic molecules was produced without using an aqueous dispersion, the master batch did not pass through the sintering filter. , A large number of agglomerated particles were present in the master batch, and the agglomeration prevention property of the metal oxide was inferior.
• Comparative Example 3 when the masterbatch (13) was manufactured without using the aqueous dispersion and the filament (13) was manufactured using the masterbatch, the yarn breakage occurred 10 times or more, and the filament The spinnability was poor. Further, in Comparative Example 3, when the masterbatch (13) was manufactured without using the aqueous dispersion and the filament (13) was manufactured using the masterbatch, 20 particles having a particle diameter of 20 ⁇ m or more in the filament were produced. As described above, a large number of agglomerated particles were present in the filament as compared with Examples 1 to 10, and the agglomeration prevention property of the metal oxide was inferior.
• Comparative Example 4 when the filament (14) was produced without using both the aqueous dispersion and the masterbatch, the yarn breakage occurred 10 times or more, and the spinnability of the filament was poor. Further, in Comparative Example 4, when the filament (14) was produced without using both the aqueous dispersion and the masterbatch, the number of particles having a particle diameter of 20 ⁇ m or more in the filament was 20 or more, which was compared with Examples 1 to 10. In addition, a large number of aggregated particles were present in the filament, and the antiaggregation property of the metal oxide was inferior.
• Comparative Example 5 when the masterbatch (13) was manufactured without using the aqueous dispersion and the film (2) was manufactured using the masterbatch, the film could not be formed even if the pressure was increased, and the film was compared with Example 11. As a result, the film-forming property of the film was inferior. Further, in Comparative Example 5, when the masterbatch (13) was manufactured without using the aqueous dispersion and the film (2) was manufactured using the masterbatch, 20 or more particles having a particle diameter of 20 ⁇ m or more in the film were produced. As compared with Example 11, a large number of agglomerated particles were present in the film, and the agglomeration prevention property of the metal oxide was inferior.

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