WO2022075395A1

WO2022075395A1 - Thermoplastic resin composition and method for producing same

Info

Publication number: WO2022075395A1
Application number: PCT/JP2021/037086
Authority: WO
Inventors: 悠太山岡; 将馬水谷; 陽介都留; 恭平高山; 敏樹木村
Original assignee: Dic株式会社
Priority date: 2020-10-08
Filing date: 2021-10-07
Publication date: 2022-04-14
Also published as: JPWO2022075395A1; JP2025023221A

Abstract

The present invention provides a master batch which is capable of improving the processability, mechanical characteristics and appearance quality of a molded article by achieving high dispersion of an inorganic compound. More specifically, this master batch contains a polyolefin resin (A), an inorganic compound that is mainly composed of a metal oxide, an amphiphilic molecule and an oxidized wax; and if the total mass of the polyolefin resin (A), the inorganic compound, the amphiphilic molecule and the oxidized wax in the master batch is taken as 100% by mass, the content of the oxidized wax is from 0.01% by mass to 25% by mass.

Description

Thermoplastic resin composition and its manufacturing method

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.

To solve this, powder dry color mixed with metal oxide and dispersant, liquid color or paste color with pigment dispersed in dispersant liquid at room temperature, metal in solid resin at room temperature. There are pellet-shaped, flake-shaped, or bead-shaped master batches in which oxides are dispersed. These compositions are used properly depending on the intended use, taking advantage of their characteristics. Of these, the masterbatch is preferably used from the viewpoint of ease of handling and preservation of the working environment at the time of use. Traditionally, as dispersants, 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.

However, for example, when a high-speed pigment dispersion is required such as spinning a thermoplastic resin at a diameter of 20 μm 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. In order to solve these problems, 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.

So far, for the purpose of improving dispersibility, for example, synthetic resin aqueous dispersion or aqueous solution (a) 1 to 80% by weight, pigment (b) 1 to 90% by weight, and thermoplastic resin (c) 1 to 90% by weight have been used. A method for producing a masterbatch, which is supplied to a twin-screw extruder and subjected to phase substitution and dehydration, has been proposed (Patent Document 1).

Further, a step (A) for producing an aqueous slurry of a pigment containing a dispersant represented by the following general formula (1), and a metallocene-based polyolefin containing a dispersant and a solvent represented by the following general formula (1). A step (C) of producing a melt, a step (C) of stirring the mixture of the water slurry obtained in the step (A) and the melt obtained in the step (B) to flush the pigment, and the step (step). 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.)

Further, 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. A pigment in which a pigment is dispersed in the melted heat-meltable resin by kneading the mixture at a temperature equal to or higher than the melting temperature of the heat-meltable resin while discharging water vapor from the vent port. A method for producing a resin composition has been proposed (Patent Document 3).

Japanese Patent No. 3158847 Japanese Patent No. 3890985 Japanese Unexamined Patent Publication No. 2014-98164

However, when the metal oxide-dispersed aqueous solution is dehydrated and dried, secondary aggregation is likely to occur due to the exposure of the active surface of the metal oxide, and it is difficult to prepare a master batch in which the metal oxide is highly dispersed. It cannot be said that the dispersibility of the metal oxide is sufficient by the conventional manufacturing method, and there is still room for improvement. In addition, since there is a need for further reduction in the diameter of the fiber and further thinning of the film, the processability and mechanical properties of the molded product when processing into a thread having a smaller fiber diameter or processing into a thinner film , There is concern about deterioration of appearance quality.

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.

In order to achieve the above objectives, 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. 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 As a result, it was found that 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.

That is, the present invention provides the following means.
[1] 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.

[2] 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 master batch according to the above [1], which is 0.01% by mass or more and 40% by mass or less.

[3] 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. The master batch according to the above [1] or [2], which comprises seeds or two or more kinds.

[4] The master batch according to the above [3], wherein the amphipathic molecule comprises one or more selected from sorbitan fatty acid ester and polyoxyethylene alkyl ether.

[5] The masterbatch according to the above [1], wherein the polyolefin resin (A) comprises one or two selected from polypropylene, high-density polyethylene, low-density polyethylene and polymethylpentene.

[6] A thermoplastic resin composition comprising the masterbatch according to any one of the above [1] to [5] and the polyolefin resin (B).

[7] 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. The thermoplastic resin composition according to the above [6].

[8] The thermoplastic resin according to the above [6] or [7], wherein the polyolefin resin (B) comprises one or two selected from polypropylene, high-density polyethylene, low-density polyethylene and polymethylpentene. Composition.

[9] A thermoplastic resin molded product obtained by melt-molding the thermoplastic resin composition according to any one of the above [6] to [8].

[10] A thermoplastic resin molded product obtained by blending the masterbatch according to any one of the above [1] to [5] with the polyolefin resin (B).

[11] 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. The thermoplastic resin molded product according to the above [10].

[12] The thermoplastic resin according to the above [10] or [11], wherein the polyolefin resin (B) comprises one or two selected from polypropylene, high-density polyethylene, low-density polyethylene and polymethylpentene. Molded body.

[13] The 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.

[14] A step (I) of mixing an inorganic compound containing a metal oxide as a main component and an amphipathic molecule to prepare an aqueous dispersion containing the inorganic compound in an amount of 1% by mass or more and 80% by mass or less. ,
A mixture (A) obtained by adjusting the content of the oxide wax to be 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. ) In the step (II) of supplying the aqueous dispersion in an amount of 1 part by mass or more and 300 parts by mass or less with respect to 100 parts by mass and melting and mixing.
A method of manufacturing a masterbatch.

[15] A method for producing a 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).

[16] With the masterbatch, 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 method for producing a thermoplastic resin composition according to the above [15], wherein the polyolefin resin (B) is melt-mixed.

[17] A method for producing a 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].

[18] A method for producing a 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).

[19] With the masterbatch, 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 method for producing a thermoplastic resin molded product according to the above [18], wherein the polyolefin resin (B) is melt-mixed.

[20] The above-mentioned [17] to [19], wherein any of filaments, staples, non-woven fabrics, hollow threads and films is molded using the masterbatch and the polyolefin resin (B). Method for manufacturing a thermoplastic resin molded article.

According to 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.

Hereinafter, embodiments of the present invention will be described. The present invention is not limited to the following embodiments.

<Masterbatch>
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.

[Polyolefin resin (A)]
When the total mass of the polyolefin resin (A), the inorganic compound, the amphoteric molecule and the oxide wax in the masterbatch is 100% by mass, 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. When 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. When 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.
Examples of such olefins include α-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 α-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-butene, 1-nonene, 1-decene, 1-undecene , 1-Dodecene and the like.

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.

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.

Further, the 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.

[Inorganic compounds]
As described above, 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. Further, the inorganic compound may be composed of one kind or two or more kinds of metal oxides.

When the total mass of the polyolefin resin (A), the inorganic compound, the amphoteric molecule and the oxide wax in the master batch is 100% by mass, 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. When 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.

[Amphiphile]
Examples of the amphipathic molecule 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.). 0), diglyceryl monoisostearate (HLB value 5.5), tetraglyceryl monostearate (HLB value 6.0), tetraglyceryl monooleate (HLB value 6.0), decaglyceryl tristearate (HLB value) 7.5), polyglycerin fatty acid esters (A) such as decaglyceryl trioleate (HLB value 7.0), decaglyceryl pentastearate (HLB value 3.5);
Hexaglyceryl monolaurate (HLB value 14.5), hexaglyceryl monomyristine (HLB value 11.0), decaglyceryl monolaurate (HLB value 15.5), decaglyceryl monomyristine (HLB value 14.0). , Decaglyceryl monostearate (HLB value 12.0), decaglyceryl monoisostearate (HLB value 12.0), decaglyceryl monooleate (HLB value 12.0), decaglyceryl diisostearate (HLB value 10.0) ) And other polyglycerin fatty acid esters (B);
-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). Esters;
-POE (3) lauryl ether (HLB value 8.0), POE (5) lauryl ether (HLB value 1.0), POE (5) isocetyl ether (HLB value 8.0), POE (3) cetyl ether (HLB value 6.0), POE (5) cetyl ether (HLB value 8.0), POE (2) stearyl ether (HLB value 8.0), POE (5) stearyl ether (HLB value 8.0), POE (6) stearyl ether (HLB value 8.0), POE (5) isostearyl ether (HLB value 8.0), POE (2) oleyl ether (HLB value 7.5), POE (3) oleyl ether (3) oleyl ether ( HLB value 6.0), POE (5) oleyl ether (HLB value 8.0), POE (5) octyldodecyl ether (HLB value 7.0), POE (5) behenyl ether (HLB value 7.0), Polyoxyethylene such as POE (5) decyltetradecyl ether (HLB value 6.0), POE (3) secondary alkyl ether (HLB value 8.0), POE (5) cholesteryl ether (HLB value 7.0) Alkyl ethers (A);
-POE (4.2) lauryl ether (HLB value 11.5), POE (7) lauryl ether (HLB value 11.0), POE (9) lauryl ether (HLB value 14.5), POE (10) lauryl Ether (HLB value 12.0), POE (12) lauryl ether (HLB value 13.0), POE (15) lauryl ether (HLB value 14.0), POE (20) lauryl ether (HLB value 15.0) , POE (30) lauryl ether (HLB value 16.0), POE (50) lauryl ether (HLB value 17.0), POE (10) isosetyl ether (HLB value 11.0), POE (15) isosetyl. Ether (HLB value 13.0), POE (20) isosetyl ether (HLB value 14.0), POE (25) isosetyl ether (HLB value 15.0), POE (5.5) cetyl ether (HLB value) 10.5), POE (7) cetyl ether (HLB value 11.5), POE (10) cetyl ether (HLB value 13.5), POE (12) cetyl ether (HLB value 12.0), POE (15) ) Cetyl ether (HLB value 15.5), POE (17) cetyl ether (HLB value 13.0), POE (20) cetyl ether (HLB value 17.0), POE (23) cetyl ether (HLB value 18. 0), POE (8) stearyl ether (HLB value 10.0), POE (11) stearyl ether (HLB value 11.0), POE (15) stearyl ether (HLB value 12.0), POE (20) stearyl Ether (HLB value 18.0), POE (25) stearyl ether (HLB value 14.0), POE (30) stearyl ether (HLB value 15.0), POE (40) stearyl ether (HLB value 16.0) , POE (10) isostearyl ether (HLB value 11.0), POE (15) isostearyl ether (HLB value 12.0), POE (20) isostearyl ether (HLB value 13.0), POE (25) Isostearyl ether (HLB value 14.0), POE (3) oleyl ether (HLB value 6.0), POE (7) oleyl ether (HLB value 10.5), POE (8) oleyl ether (HLB value 10.). 0), POE (10) oleyl ether (HLB value 14.5), POE (12) oleyl ether (HLB value 11.0), POE (15) oleyl ether (HLB value 16.0), PO E (20) oleyl ether (HLB value 17.0), POE (23) oleyl ether (HLB value 14.0), POE (50) oleyl ether (HLB value 18.0), POE (10) octyldodecyl ether (10) HLB value 10.0), POE (16) octyldodecyl ether (HLB value 12.0), POE (20) octyldodecyl ether (HLB value 13.0), POE (25) octyldodecyl ether (HLB value 14.0) ), POE (25) octyldodecyl ether (HLB value 14.0), POE (10) behenyl ether (HLB value 10.0), POE (20) behenyl ether (HLB value 16.5), POE (30) behenyl Ether (HLB value 18.0), POE (15) decyltetradecyl ether (HLB value 11.0), POE (20) decyltetradecyl ether (HLB value 12.0), POE (25) decyltetradecyl ether (HLB value 12.0) HLB value 13.0), POE (4) (C12-15) alkyl ether (HLB value 10.5), POE (8) (C9-11) alkyl ether (HLB: 13.9), POE (10) ( C12-15) Alkyl ether (HLB value 15.5), POE (5) Secondary alkyl ether (HLB value 10.5), POE (7) Secondary alkyl ether (HLB value 12.0), POE (10) Cholesteryl ether (HLB value 10.0), POE (15) Cholesteryl ether (HLB value 11.0), POE (20) Cholesteryl ether (HLB value 12.0), POE (24) Cholesteryl ether (HLB value 13.0) ), POE (30) cholesteryl ether (HLB value 14.0) and other polyoxyethylene alkyl ethers (B);
-POE (2) laurylamine (HLB value 5.2), POE (2) stearylamine (HLB value 5.1), POE (3) beef propylene diamine (HLB value 5.9), N-bis-N- Polyoxyethylene alkylamines (A) such as cyclohexylamine (HLB value 4.8), POE (2) metaxylene diamine (HLB value 7.9);
POE (5) laurylamine (HLB value 10.4), POE (7) laurylamine (HLB value 12.1), POE (10) laurylamine (HLB value 13.6), POE (30) laurylamine ( HLB value 17.5), POE (7) ethylene beef amine (HLB value 11.0), POE (8) ethylene beef amine (HLB value 11.9), POE (10) ethylene beef amine (HLB value 12.7) ), POE (13.5) ethylene beef amine (HLB value 11.0), POE (20) ethylene beef amine (HLB value 15.5), POE (30) ethylene beef amine (HLB value 16.7), POE (40) Ethylene beef amine (HLB value 17.4), POE (7) stearylamine (HLB value 10.7), POE (10) stearylamine (HLB value 12.8), POE (15) stearylamine (HLB) Value 14.3), POE (20) stearylamine (HLB value 15.3), POE (30) stearylamine (HLB value 16.7), POE (45) stearylamine (HLB value 17.6), POE ( 15) Polyoxyethylene alkylamines such as beef propylene diamine (HLB value 13.4), POE (50) stearyl propylene diamine (HLB value 17.4), POE (4) metaxylenediamine (HLB value 11.3). (B);
Polyoxyethylene alkyl amides such as POE (50) stearyl amide (HLB value 17.8).

For example, when "POE (8) (C9-11) alkyl ether" is described, "POE" is polyoxyethylene, "(8)" is m in the following general formula (2), and "alkyl (C9)" is used. -11) Alkyl "means an alkyl mixture having 9 to 11 carbon atoms.
R- (CH ₂ CH ₂ O) _m -H ... (2)

Further, one selected from these amphipathic molecules may be used alone, or two or more thereof may be used in combination.

When the total mass of the polyolefin resin (A), the inorganic compound, the amphipathic molecule and the oxide wax in the master batch is 100% by mass, 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. When 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.

When two types of amphipathic molecules of different types (for example, HLB) are used as the amphipathic molecule, 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. Thereby, both the action of compatibilizing the inorganic compound with the polyolefin resin (A) and the action of stabilizing the dispersion of the inorganic compound in the polyolefin resin (A) can be exhibited in a well-balanced manner.

[Oxidation wax]
When the total mass of the polyolefin resin (A), the inorganic compound, the amphoteric molecule and the oxide wax in the masterbatch is 100% by mass, 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. When 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.

Further, one kind selected from these oxide waxes may be used alone, or two or more kinds may be used in combination.

[Other ingredients]
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 molded product>
The 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.

[Polyolefin resin (B)]
When the total mass of the masterbatch and the polyolefin (B) in the thermoplastic resin composition or the molded body is 100% by mass, 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 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.

[Amphiphile]
Further, when the total mass of the masterbatch and the polyolefin resin (B) in the thermoplastic resin molded body is 100% by mass, 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.

Further, when two types of amphipathic molecules of different types (for example, HLB) are used as the amphipathic molecules, the amphipathic molecule (A) and the amphipathic molecule (B) in the thermoplastic resin composition or the molded product are used. ) Is preferably an amphipathic molecule (A): amphipathic molecule (B) = 10 to 90: 90 to 10, and more preferably 20 to 80: 80 to 20.

[Oxidation wax]
When the total mass of the masterbatch and the polyolefin resin (B) in the thermoplastic resin composition or the molded body is 100% by mass, 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.

[Other ingredients]
The 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. Further, the thermoplastic resin molded product may be a film.

<Manufacturing method of masterbatch>
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. When the total mass of the body preparation step (I) and the polyolefin resin (A) and the oxide wax is 100% by mass, the content of the oxide wax is 0.01% by mass or more and 20% by mass or less. With respect to 100 parts by mass of the mixture (A) obtained in accordance with the above, 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.

When the total mass of the inorganic compound, the amphoteric molecule and water in the aqueous dispersion used in the step (I) is 100% by mass, 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.

When the total mass of the inorganic compound, the amphipathic molecule and water in the aqueous dispersion is 100% by mass, 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. When 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).

When the total mass of the polyolefin resin (A) and the oxide wax in the mixture (A) is 100% by mass, 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.

When the total mass of the polyolefin resin (A) and the oxide wax in the mixture (A) is 100% by mass, 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.

In the above step (I), 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.

In this case, 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. Is 1% by mass or more and 80% by mass or less, and the content of the inorganic compound may be more preferably 1% by mass or more and 70% by mass or less, and further 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.

When the total mass of the inorganic compound, the amphipathic molecule, the water-soluble alcohol and water in the aqueous dispersion is 100% by mass, 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. When the content of the amphipathic molecule 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).

When the total mass of the inorganic compound, the amphoteric molecule, the water-soluble alcohol and water in the aqueous dispersion is 100% by mass, 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. When 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.

[Other ingredients]
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.

In the step (II), 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. If 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. On the other hand, when 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.

In the mixture (B) of the mixture (A) and the aqueous dispersion, 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.

When the total mass of the mixture (A) and the aqueous dispersion in the mixture (B) is 100% by mass, 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.

For melt mixing, a kneader such as an extruder (single-screw extruder, twin-screw extruder), kneader, or Banbury mixer can be used. Among them, 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. or lower, still more preferably 220 ° C. or lower. When 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. When the heating temperature is 240 ° C. or lower, thermal deterioration of each component can be suppressed.

In the above step (II), an aqueous dispersion containing a water-soluble alcohol may be used. In this case, 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. By using an aqueous dispersion containing a water-soluble alcohol, the dispersion of the inorganic compound in (A) can be made more stable.

When the aqueous dispersion contains a water-soluble alcohol, 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.

In this case, 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.

After melt-mixing, the masterbatch can be molded or processed into a shape (for example, pellet form) according to the purpose of use.
When the masterbatch is pelletized, after melt-kneading, strands are formed, and the strands are cut with a pelletizer to be pelletized. 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.).

<Manufacturing method of 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. 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.

When the total mass of the masterbatch and the polyolefin resin (B) is 100% by mass, 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. Hereinafter, it is preferable to melt-mix the masterbatch and the polyolefin resin (B) so as to be in the range of 1% by mass or more and 70% by mass or less, more preferably. When 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.

In the melt mixing step, components other than the masterbatch and the polyolefin resin (B) may be further mixed. For example, in the mixing step, the antioxidant can be mixed with the masterbatch and the polyolefin resin (B).

After melt-mixing, 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.
When the thermoplastic resin molded body is in the form of threads (filaments, staples, hollow threads), after melt-kneading, 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.
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.
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.

Hereinafter, embodiments of the present invention will be described. The present invention is not limited to the examples shown below. In the examples, unless otherwise specified, "part" indicates mass%, and the unit of the numerical value in the table is mass part.

[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.

(Manufacturing of masterbatch)
Polypropylene ("Y-2000GV" manufactured by Prime Polymer Co., Ltd.) 90 parts by mass and 10 parts by mass of oxide wax ("High Wax 4052E" manufactured by Mitsui Chemicals, Inc.) 30 mmφ biaxial vent type extruder (set temperature 230 ° C, capture It was melt-kneaded in a mesh filter having a particle diameter of 40 μm), and 30 parts by mass of the aqueous dispersion (1) was injected from the liquid addition nozzle from the upstream part of the extruder, and melt-kneaded while evaporating the water from the vent port. The obtained thermoplastic resin composition was pelletized to obtain a masterbatch (1).

(Manufacturing of filament)
Masterbatch (1) 10 parts by mass is mixed with 90 parts by mass of polypropylene ("Y-2000GV" manufactured by Prime Polymer Co., Ltd.), melt spinning is performed at a spinning temperature of 230 ° C. using a spinning machine, and 3dtex (3dtex) is performed by triple stretching. A filament (1) having a fiber diameter of about 15 μm) was obtained.

[Example 2]
(Manufacturing of aqueous dispersion)
The same procedure as in Example 1 was carried out except that the 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.

(Manufacturing of masterbatch)
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).

(Manufacturing of filament)
The same procedure as in Example 1 was carried out except that the masterbatch (1) was changed to the masterbatch (2), to obtain a filament (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).

(Manufacturing of masterbatch)
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).

(Manufacturing of filament)
The same procedure as in Example 1 was carried out except that the masterbatch (1) was changed to the masterbatch (3), to obtain a filament (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.

(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.

(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 same procedure as in Example 1 was carried out except that 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).

(Manufacturing of masterbatch)
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).

(Manufacturing of filament)
The same procedure as in Example 1 was carried out except that the masterbatch (1) was changed to the masterbatch (6) to obtain a filament (6).

[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).

(Manufacturing of masterbatch)
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).

(Manufacturing of filament)
The same procedure as in Example 1 was carried out except that the masterbatch (1) was changed to the masterbatch (7), to obtain a filament (7).

[Example 8]
(Manufacturing of masterbatch)
The same procedure as in Example 1 was carried out except that 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.

(Manufacturing of filament)
Masterbatch (8) 10 parts by mass is mixed with 90 parts by mass of linear low-density polyethylene (“Novatec LL UJ580” manufactured by Nippon Polyethylene Co., Ltd.) changed from polypropylene, and melt-spun at a spinning temperature of 150 ° C. using a spinning machine. Was performed, and a 3dtex filament (8) was obtained by 3-fold stretching.

[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).

(Manufacturing of filament)
90 parts by mass of high-density polyethylene ("Suntech HD J320" manufactured by Asahi Kasei Co., Ltd.) changed from polypropylene is mixed with 10 parts by mass of masterbatch (9), and melt spinning is performed at a spinning temperature of 150 ° C. using a spinning machine. Filament (9) of 3dtex was obtained by double stretching.

[Example 10]
(Manufacturing of masterbatch)
The same procedure as in Example 1 was carried out except that 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.

(Manufacturing of filament)
Mix 10 parts by mass of master batch (9) with 90 parts by mass of poly-4-methyl-1-pentene (“TPX DX818” manufactured by Mitsui Chemicals, Inc.) changed from polypropylene, and use a spinning machine at a spinning temperature of 280 ° C. Melt spinning was performed and 3-fold stretching was performed to obtain a filament (10) of 3 dtex.

[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 μm was obtained.

[Comparative Example 1]
(Manufacturing of aqueous dispersion, masterbatch and filament)
The same procedure as in Example 1 was carried out except that polyoxyethylene alkyl ether as an amphipathic molecule was not used to obtain an aqueous dispersion (6), a masterbatch (11) and a filament (12).

[Comparative Example 2]
(Manufacturing of masterbatch and filament)
The same procedure as in Example 1 was carried out except that the oxide wax was changed to 30 parts by mass to obtain a master batch (12) and a filament (12).

[Comparative Example 3]
(Manufacturing of masterbatch and filament)
No aqueous dispersion is used, and 9 parts by mass of titanium oxide particles, 0.3 parts by mass of polyoxyethylene alkyl ether, 0.3 parts by mass of sorbitan fatty acid ester and 0.3 parts by mass of ethanol are directly added to polypropylene (Prime Polymer Co., Ltd.). Manufactured by "Y-2000GV") 81.09 parts by mass and 9.01 parts by mass of oxide wax were mixed and melt-kneaded with a twin-screw extruder to prepare a master batch (13), which was the same as in Example 1. Filament (13) was obtained through the steps.

[Comparative Example 4]
(Manufacturing of filament)
Both the aqueous dispersion and the master batch are not used, and 0.9 parts by mass of titanium oxide particles, 0.03 parts by mass of polyoxyethylene alkyl ether, 0.03 parts by mass of sorbitan fatty acid ester and 0.03 parts by mass of ethanol are directly used. , Polypropylene (“Y-2000GV” manufactured by Prime Polymer Co., Ltd.) was mixed with 99.01 parts by mass and melt-kneaded with a spinning machine to obtain a filament (14) through the same steps as in Example 1.

[Comparative Example 5]
(Manufacturing of film)
10 parts by mass of masterbatch (13) was mixed with 90 parts by mass of polypropylene (“Y-2000GV” manufactured by Prime Polymer Co., Ltd.), vacuum dried at 150 ° C. for 12 hours, and then 20 mm with a 100 mm wide T-die connected. A melt film was formed at a film forming temperature of 280 ° C. using a single-screw extruder to obtain a film (2) having a thickness of 10 μm.

Next, each masterbatch, filament and film obtained in Examples 1 to 11 and Comparative Examples 1 to 5 were measured and evaluated by the following methods.

1. 1. Evaluation of aggregated particles in the masterbatch (anti-aggregation)
For the obtained master batches (1) to (13), a sintered filter with a filtration diameter of 25 μm was installed at the screw tip of a 25 mm single-screw extruder, and the differential pressure when 1 kg of the master batch was passed was measured. When the differential pressure is 1 MPa or less, it is very good "◎", when it is 1 to 5 MPa or less is good "○", when it exceeds 5 MPa and 10 MPa or less is slightly defective "△", and when it does not pass, it is defective "×". ..

2. 2. Evaluation of Filament Spinnability 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 "Δ", and the case of 10 times or more was regarded as a defective "x".

3. 3. Evaluation of aggregated particles in filament (anti-aggregation)
0.1 g of the obtained filaments (1) to (14) were cut out, pressed into a film with a slide, and then observed with an optical microscope (magnification 200 times) to obtain particle images, and at least 1000 randomly selected particles were obtained. The particle size (equivalent to a circle) was measured for each of the particles (which may be primary particles or may further contain secondary particles). Very good when there is less than one particle with a particle diameter of 20 μm or more "◎", 1 to 5 are good "○", 6 to 19 are slightly defective "△", 20 or more are defective "×" And said.

4. Evaluation of film-forming property The stability of the obtained films (1) and (2) during film-forming was evaluated. A sintered filter having a filtration diameter of 20 μm was installed, and a film was formed for 10 kg of the raw material to evaluate the workability. The case where the film formation was completed without boosting was evaluated as good "○", the case where the film formation was completed after boosting was evaluated as "△", and the case where the film formation could not be completed even after the pressure was increased was evaluated as "×".

5. Evaluation of aggregated particles in film (anti-aggregation property)
0.1 g of the obtained films (1) and (2) were cut out, pressed into a film with a slide, and then observed with an optical microscope (magnification 200 times) to obtain particle images, and at least 1000 randomly selected particles were obtained. The particle size (equivalent to a circle) was measured for each of the particles (which may be primary particles or may further contain secondary particles). Very good when there is less than one particle with a particle diameter of 20 μm or more "◎", 1 to 5 are good "○", 6 to 19 are slightly defective "△", 20 or more are defective "×" And said.

The results of measurement and evaluation by the above method are shown in Tables 1A and 2.

From the results of Tables 1A to 1C, in Examples 1 to 10, the aqueous dispersions (1) to (5) containing one or two of polyoxyethylene alkyl ether and sorbitan fatty acid ester as amphipathic molecules. ), And the total mass of polypropylene as the polyolefin resin (A) and polyethylene wax as the oxide wax is 100% by mass, the content of the polyethylene wax is 0.1% by mass or more and 20% by mass or less. When polypropylene and polyethylene wax are mixed to produce master batches (1) to (10) as described above, the differential pressure of the master batch is 5 MPa or less, secondary aggregation of metal oxides is prevented during master batch molding, and the metal is metal. It was found that the dispersion stability of the oxide was high. In particular, in Examples 3, 6 and 7, 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. When 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, and the dispersion stability of the metal oxide is extremely high. It turned out.

Further, in Examples 1 to 10, 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. When (10) was produced, the occurrence of yarn breakage was less than 3 times, and the spinnability of the filament was good.
Further, in Examples 1 to 10, 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. When (10) was produced, it was found that the number of particles having a particle diameter of 20 μm 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. .. In particular, in 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 μm 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.

In 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 μm 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.

On the other hand, from the results in Table 2, in Comparative Example 1, when the masterbatch (11) was produced using the aqueous dispersion (6) containing no amphipathic molecule, the masterbatch did not pass through the sintering filter and the masterbatch was mastered. A large number of agglomerated particles were present in the batch, and the agglomeration prevention property of the metal oxide was inferior.

Further, in 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 μm 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.

In 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. When 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.

Further, in 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 μm 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.

In 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.

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, 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 μm 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.

In 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 μm 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.

In 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 μm 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.

Claims

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.
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 amphipathic molecule is 0.01 mass by mass. The master batch according to claim 1, wherein the content is% or more and 40% by mass or less.
The amphoteric molecule is one or 2 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. The master batch according to claim 1 or 2, which comprises seeds or more.
The master batch according to claim 3, wherein the amphipathic molecule comprises one or more selected from sorbitan fatty acid ester and polyoxyethylene alkyl ether.
The masterbatch according to claim 1, wherein the polyolefin resin (A) comprises one or two selected from polypropylene, high-density polyethylene, low-density polyethylene and polymethylpentene.
A thermoplastic resin composition comprising the masterbatch according to any one of claims 1 to 5 and the polyolefin resin (B).
Claimed that 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) in the thermoplastic resin molded product is 100% by mass. Item 6. The thermoplastic resin composition according to Item 6.
The thermoplastic resin composition according to claim 6 or 7, wherein the polyolefin resin (B) comprises one or two selected from polypropylene, high-density polyethylene, low-density polyethylene, and polymethylpentene.
A thermoplastic resin molded product obtained by melt-molding the thermoplastic resin composition according to any one of claims 6 to 8.
A thermoplastic resin molded product obtained by blending the masterbatch according to any one of claims 1 to 5 with the polyolefin resin (B).
Claimed that 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) in the thermoplastic resin molded product is 100% by mass. Item 10. The thermoplastic resin molded product according to Item 10.
The thermoplastic resin molded body according to claim 10 or 11, wherein the polyolefin resin (B) comprises one or two selected from polypropylene, high-density polyethylene, low-density polyethylene and polymethylpentene.
The thermoplastic resin molded product according to any one of claims 9 to 12, wherein the thermoplastic resin molded product is selected from filaments, staples, non-woven fabrics, hollow threads, and films.
A step (I) of mixing an inorganic compound containing a metal oxide as a main component and an amphipathic molecule to prepare an aqueous dispersion containing the inorganic compound in an amount of 1% by mass or more and 80% by mass or less.
100% by mass of the mixture obtained by adjusting the content of the oxide wax to be 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. The step (II) in which the aqueous dispersion is supplied in an amount of 1 part by mass or more and 300 parts by mass or less and melt-mixed.
A method of manufacturing a masterbatch.
A method for producing a thermoplastic resin composition, which comprises a step of melting and mixing the masterbatch obtained by the production method according to claim 14 and the polyolefin resin (B).
When the total mass of the masterbatch and the polyolefin resin (B) is 100% by mass, the masterbatch and the polyolefin resin have a content of 1% by mass or more and 90% by mass or less. The method for producing a thermoplastic resin composition according to claim 15, wherein (B) is melt-mixed.
A method for producing a thermoplastic resin molded product, which comprises a step of melt-molding the thermoplastic resin composition obtained by the production method according to claim 15 or 16.
A method for producing a thermoplastic resin molded product, which comprises a step of melting and mixing the masterbatch obtained by the production method according to claim 14 and the polyolefin resin (B).
When the total mass of the masterbatch and the polyolefin resin (B) is 100% by mass, the masterbatch and the polyolefin resin have a content of 1% by mass or more and 90% by mass or less. The method for producing a thermoplastic resin molded product according to claim 18, wherein (B) is melt-mixed.
The thermoplastic resin according to any one of claims 17 to 19, wherein the masterbatch and the polyolefin resin (B) are used to form any one selected from filaments, staples, non-woven fabrics, hollow threads and films. A method for manufacturing a molded product.