CN116348536A

CN116348536A - Thermoplastic resin composition and method for producing same

Info

Publication number: CN116348536A
Application number: CN202180068856.0A
Authority: CN
Inventors: 山冈悠太; 水谷将马; 都留阳介; 高山恭平; 木村敏树
Original assignee: DIC Corp
Current assignee: DIC Corp
Priority date: 2020-10-08
Filing date: 2021-10-07
Publication date: 2023-06-27
Also published as: JPWO2022075392A1; WO2022075392A1

Abstract

Providing: a master batch which can realize high dispersion of inorganic compounds and improve the processability, mechanical properties and appearance quality of molded articles. In more detail, the masterbatch contains: a thermoplastic resin (A), an inorganic compound containing a metal oxide as a main component, an amphipathic molecule (A) having an HLB value in the range of 1 to 8, and an amphipathic molecule (B) having an HLB value in the range of 10 to 18.

Description

Thermoplastic resin composition and method for producing same

Technical Field

The present invention relates to a thermoplastic resin composition and a method for producing the thermoplastic resin composition.

Background

Metal oxides have been used for various purposes because of their high activity. However, it is known that when a metal oxide is used for a polymer composite material, the dispersion of the metal oxide becomes difficult due to its high aggregation.

To solve this problem, there are: a powdery dry pigment in which a metal oxide and a dispersant are mixed, a liquid pigment or a pasty pigment in which a pigment is dispersed in a dispersant which is liquid at ordinary temperature, a master batch in which a metal oxide is dispersed in a resin which is solid at ordinary temperature, and the like are provided. These compositions are used separately by taking advantage of their characteristics according to the application, but among them, a master batch is preferably used in view of ease of handling and work environment preservation at the time of use. In order to impart dispersibility to the metal oxide in the master batch, conventionally, 1 or 2 or more of stearic acid, zinc stearate, magnesium stearate, aluminum stearate, calcium stearate, ethylene bisamide, polyethylene wax, polypropylene wax, and wax formed of a derivative thereof, for example, an acid-modified body, have been used as a dispersant.

However, for example, when a thermoplastic resin is spun at a high speed of 20 μm or less in fiber diameter, or a pigment having a high degree of film formation is dispersed, the dispersion cannot be satisfied in some cases by the above-mentioned dispersant. That is, yarn breakage during spinning due to dispersion failure, clogging of a filter of a melt spinning machine, poor molding in a film, and the like are caused. In order to solve these problems, attempts have been made to improve the dispersibility by a powerful mixer by improving the processing method of the master batch, but sufficient dispersibility cannot be exhibited.

Heretofore, for the purpose of improving dispersibility, for example, a method for producing a master batch has been proposed in which a synthetic resin aqueous dispersion or aqueous solution (a) is supplied to a twin-screw extruder in an amount of 1 to 80% by weight, a pigment (b) in an amount of 1 to 90% by weight, and a thermoplastic resin (c) in an amount of 1 to 90% by weight, and phase substitution and dehydration are performed (patent document 1).

In addition, a method for producing a colored resin composition is proposed, which comprises the steps of: a step (A) of producing an aqueous slurry of a pigment containing a dispersant represented by the following general formula (1); a step (B) of producing a melt of a metallocene polyolefin containing a dispersant represented by the following general formula (1) and a solvent; a step (C) of stirring the mixture of the aqueous slurry obtained in the step (A) and the melt obtained in the step (B) to flush the pigment; and a step (D) of removing the solvent and water from the rinsed mixture obtained in the step (C) (patent document 2).

C _n H _2n+1 (OCH ₂ CH ₂ ) _m OH···(1)

(wherein n is an integer of 1 to 100 and m is an integer of 1 to 100.)

Further, a method for producing a pigment/resin composition is proposed, which comprises the steps of: mixing an aqueous slurry containing a pigment with a hot-melt resin to prepare a mixture of moisture, a pigment and the hot-melt resin, dehydrating the mixture, adjusting the content of moisture in the mixture to 4 to 25 mass%, continuously feeding the mixture into an extrusion kneader having at least 1 vent, kneading the mixture at a temperature equal to or higher than the melting temperature of the hot-melt resin, discharging the separated moisture and the water vapor of the residual moisture from the vent, and kneading the mixture at a temperature equal to or higher than the melting temperature of the hot-melt resin to obtain a pigment/resin composition in which the pigment is dispersed in the molten hot-melt resin (patent document 3).

Prior art literature

Patent literature

Patent document 1: japanese patent No. 3158847

Patent document 2: japanese patent No. 3890985

Patent document 3: japanese patent laid-open publication No. 2014-98164

Disclosure of Invention

Problems to be solved by the invention

However, if the aqueous metal oxide dispersion solution is dehydrated and dried, secondary aggregation tends to occur due to 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. Further, there is a demand for further reduction in diameter of fibers and further reduction in film thickness, and therefore, there is a concern that the processability, mechanical properties, appearance quality and the like of a molded article are reduced when processed into filaments having smaller fiber diameters and thinner films.

The purpose 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 article.

Solution for solving the problem

In order to achieve the above object, the inventors have intensively studied and found that: regarding the HLB (hydrophilic-lipophilic balance, hydrophile Lipophile Balance) value of the dispersant, a masterbatch is produced from an aqueous dispersion containing 2 kinds of amphiphilic molecules having HLB values within specific ranges, respectively, and the obtained masterbatch is mixed with a base resin to obtain a thermoplastic resin composition or a thermoplastic resin molded article, whereby aggregation of an inorganic compound in the aqueous dispersion as an inorganic compound slurry is prevented, and as a result, the inorganic compound is highly dispersed in the masterbatch, and the processability, mechanical properties, and appearance quality of the thermoplastic resin molded article can be improved.

Namely, the present invention provides the following means.

[1] A masterbatch, comprising:

thermoplastic resin (A),

An inorganic compound containing a metal oxide as a main component,

An amphipathic molecule (A) having an HLB (hydrophilic-lipophilic balance, hydrophile Lipophile Balance) value in the range of 1 to 8, and

An amphipathic molecule (B) having an HLB value in the range of 10 to 18.

[2] The master batch according to the above [1], wherein the content of the amphiphilic molecule (A) is 0.01 mass% or more and 40 mass% or less, and the content of the amphiphilic molecule (B) is 0.01 mass% or more and 40 mass% or less, based on 100 mass% of the total mass of the thermoplastic resin (A), the inorganic compound, the amphiphilic molecule (A) and the amphiphilic molecule (B) in the master batch.

[3] The master batch according to the above [1] or [2], wherein the amphiphilic molecule (A) contains 1 or 2 or more selected from the group consisting of glycerin fatty acid esters, polyglycerin fatty acid esters, polyoxyethylene glycerin fatty acid esters, propylene glycol fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, fatty acid alkanolamides, polyoxyethylene lanolin/lanolin alcohol/beeswax derivatives, polyoxyethylene castor oil/hydrogenated castor oil, polyoxyethylene alkyl ethers, polyoxyethylene fatty acid esters, polyoxyethylene alkylamines, polyoxyethylene cetyl ethers, polyoxyethylene stearyl ether stearate, polyoxyethylene lauryl ether stearate, POE hydrogenated castor oil fatty acid esters, and polyoxyethylene trimethylolpropane fatty acid esters.

[4] The master batch according to the above [3], wherein the amphiphilic molecule (A) contains 1 or 2 kinds selected from the group consisting of polyglycerin fatty acid esters and fatty acid alkanolamides.

[5] The master batch according to any one of [1] to [4], wherein the amphiphilic molecule (B) contains 1 or 2 or more selected from the group consisting of polyglycerin fatty acid esters, polyoxyethylene glycerin fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, polyoxyethylene lanolin/lanolin alcohol/beeswax derivatives, polyoxyethylene castor oil/hydrogenated castor oil, polyoxyethylene sterols/hydrogenated sterols, polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene fatty acid esters, polyoxyethylene alkylamines, polyoxyethylene alkylamides, polyoxyethylene glycerin monostearate, POE hydrogenated castor oil fatty acid esters, polyoxyethylene trimethylolpropane fatty acid esters, and sucrose fatty acid esters.

[6] The master batch according to the above [5], wherein the amphiphilic molecule (B) contains 1 or 2 kinds selected from polyoxyethylene sorbitol fatty acid esters and polyoxyethylene alkyl ethers.

[7] The master batch according to the above [1], wherein the thermoplastic resin (A) contains 1 or more selected from the group consisting of polyethylene terephthalate, polyamide 6, polypropylene, low-density polyethylene and polycarbonate.

[8] A thermoplastic resin composition comprising the master batch of any one of [1] to [7] and a thermoplastic resin (B).

[9] The thermoplastic resin composition according to the above [8], wherein the content of the masterbatch is 1 mass% or more and 90 mass% or less, based on 100 mass% of the total mass of the masterbatch and the thermoplastic resin (B) in the thermoplastic resin composition.

[10] The thermoplastic resin composition according to the above [8] or [9], wherein the thermoplastic resin (B) contains 1 or more selected from the group consisting of polyethylene terephthalate, polyamide 6, polypropylene, linear low density polyethylene and polycarbonate.

[11] A thermoplastic resin molded article obtained by melt molding the thermoplastic resin composition according to any one of the above [8] to [10 ].

[12] A thermoplastic resin molded article obtained by blending the master batch of any one of the above [1] to [7] with a thermoplastic resin (B).

[13] The thermoplastic resin molded body according to the above [12], wherein the content of the masterbatch is 1 mass% or more and 90 mass% or less, based on 100 mass% of the total mass of the masterbatch and the thermoplastic resin (B) in the thermoplastic resin molded body.

[14] The thermoplastic resin molded article according to the above [12] or [13], wherein the thermoplastic resin (B) contains 1 or more selected from the group consisting of polyethylene terephthalate, polyamide 6, polypropylene, linear low density polyethylene and polycarbonate.

[15] The thermoplastic resin molded body according to any one of the above [11] to [14], wherein the thermoplastic resin molded body is any one selected from the group consisting of filaments, staple fibers, nonwoven fabrics, hollow fibers and films.

[16] A method for producing a master batch, comprising the steps of:

a step (I) of mixing an inorganic compound containing a metal oxide as a main component, an amphipathic molecule (A) having an HLB value in the range of 1 to 8, and an amphipathic molecule (B) having an HLB value in the range of 10 to 18, and preparing an aqueous dispersion containing 1 to 80 parts by mass of the inorganic compound; and, a step of, in the first embodiment,

and (II) supplying the aqueous dispersion in an amount of 1 to 300 parts by mass based on 100 parts by mass of the thermoplastic resin (A) and melt-mixing the aqueous dispersion.

[17] A method for producing a thermoplastic resin composition, comprising the steps of: the masterbatch obtained by the production method described in the above [16] is melt-mixed with the thermoplastic resin (B).

[18] The method of producing a thermoplastic resin composition according to the above [17], wherein the master batch and the thermoplastic resin (B) are melt-mixed so that the content of the master batch is 1 mass% or more and 90 mass% or less, based on 100 mass% of the total mass of the master batch and the thermoplastic resin (B).

[19] A method for producing a thermoplastic resin molded body, comprising the steps of: the thermoplastic resin composition obtained by the production method described in the above [17] or [18], is melt-molded.

[20] A method for producing a thermoplastic resin molded body, comprising the steps of: the masterbatch obtained by the production method described in the above [16] is melt-mixed with the thermoplastic resin (B).

[21] The method for producing a thermoplastic resin molded article according to [20] above, wherein the master batch and the thermoplastic resin (B) are melt-mixed so that the content of the master batch is 1 mass% or more and 90 mass% or less, based on 100 mass% of the total mass of the master batch and the thermoplastic resin (B).

[22] The method for producing a thermoplastic resin molded article according to any one of the above [19] to [21], wherein the thermoplastic resin (B) is molded into any one selected from the group consisting of filaments, short fibers, nonwoven fabrics, hollow fibers and films by using the master batch.

ADVANTAGEOUS EFFECTS OF INVENTION

According to the present invention, high dispersion of the inorganic compound can be achieved, and the processability, mechanical properties, and appearance quality of the molded article can be improved.

Detailed Description

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

< masterbatch >)

The master batch (also referred to as a thermoplastic resin composition) of the present embodiment contains: a thermoplastic resin (A), an inorganic compound containing a metal oxide as a main component, an amphipathic molecule (A) having an HLB value in the range of 1 to 8, and an amphipathic molecule (B) having an HLB value in the range of 10 to 18.

[ thermoplastic resin (A) ]

The content of the thermoplastic resin (a) in the master batch is preferably 30 mass% or more, more preferably 40 mass% or more, still more preferably 50 mass% or more, and may be preferably 99 mass% or less, based on 100 mass% of the total mass of the thermoplastic resin (a), the inorganic compound, the amphiphilic molecule (a), and the amphiphilic molecule (B). If the content of the thermoplastic resin (a) is 30 mass% or more, the thermoplastic resin (a) as a matrix resin becomes appropriate for the inorganic compound, and the inorganic compound becomes easier to be highly dispersed in the master batch, and if it is 99 mass% or less, the inorganic compound becomes appropriate, and the desired properties of the inorganic compound become easier to be exhibited. Therefore, the content of the thermoplastic resin (a) is set to a value within the above range.

The thermoplastic resin (a) is not particularly limited, and examples thereof include polyolefin resins such as polyethylene, polypropylene, poly (4-methyl-1-pentene) and poly (1-butene); polyester resins such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate; polyamide resins such as polyamide-6 (nylon-6), polyamide 66 (nylon-66), and poly (m-xylylenediamine) adipamide; ethylene/unsaturated ester copolymers such as ethylene/vinyl ester copolymers and ethylene/unsaturated carboxylic acid ester copolymers; ethylene/unsaturated carboxylic acid-based copolymer or ionomer resin thereof; poly (meth) acrylic resins such as poly (meth) acrylate resins; chlorine-based resins such as polyvinyl chloride and polyvinylidene chloride; fluorine-based resins such as polytetrafluoroethylene, ethylene tetrafluoroethylene copolymer, polyvinylidene fluoride and polyvinylidene fluoride; a polystyrene resin; polyether-based resins such as polyether-ether-ketone resins and polyether-ketone resins; a polycarbonate resin; polyphenylene resins such as polyphenylene ether resins and polyphenylene sulfide resins; a polyvinyl acetate resin; a polyacrylonitrile resin; thermoplastic elastomers, and the like. In addition, it is possible to use 1 kind selected from these thermoplastic resins alone, or to use 2 kinds or more in combination.

The polyolefin resin is a polyolefin resin obtained by polymerizing at least 1 olefin, and may be a homopolymer or a copolymer.

Examples of such olefins include ethylene, propylene, isobutylene, and α -olefins having 4 to 12 carbon atoms including isobutylene (1-butene), butadiene, isoprene, (meth) acrylate, (meth) acrylic acid, (meth) acrylamide, vinyl alcohol, vinyl acetate, vinyl chloride, styrene, and acrylonitrile.

Examples of the α -olefin having 4 to 12 carbon atoms include 1-butene, 2-methyl-1-propene, 2-methyl-1-butene, 3-methyl-1-butene, 1-hexene, 2-ethyl-1-butene, 2, 3-dimethyl-1-butene, 2-methyl-1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 3-dimethyl-1-butene, 1-heptene, 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, and 1-dodecene.

Examples of the polyolefin-based resin include polyethylene resin, polypropylene resin, polyisobutylene (Polyisobutene) resin, polyisobutylene (polyisopren) resin, polybutadiene resin, and the like. Among these resins, polyethylene resins and polypropylene resins 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), ultra high molecular weight polyethylene (UHMW-PE) may be mentioned, and among them, high density polyethylene is preferable.

From the viewpoint of molding into filaments or films, the thermoplastic resin (a) preferably contains 1 or 2 or more kinds selected from polypropylene, high-density polyethylene, polyethylene terephthalate, polyamide-6, and polycarbonate.

[ inorganic Compounds ]

The inorganic compound contains a metal oxide as a main component as described above. The main component is that the metal oxide is more than 50 mass% based on 100 mass% of the entire inorganic compound. The inorganic compound may be formed of 1 or 2 or more kinds of metal oxides.

The content of the inorganic compound in the masterbatch may be preferably in a range of 1 mass% or more, and may be preferably in a range of 70 mass% or less, more preferably 60 mass% or less, and still more preferably 50 mass% or less, based on 100 mass% of the total mass of the thermoplastic resin (a), the inorganic compound, the amphiphilic molecule (a), and the amphiphilic molecule (B). If the content of the inorganic compound is 1 mass% or more, the desired properties of the inorganic compound are easily exhibited, and if it is 70 mass% or less, the inorganic compound is easily uniformly dispersed in the master batch.

The inorganic compound is not particularly limited, and examples thereof include metal oxides such as titanium (Ti), silicon (Si), zinc (Zn), aluminum (Al), copper (Cu), iron (Fe), molybdenum (Mo), and zirconium oxide (Zr). In addition, 1 kind selected from these inorganic compounds may be used alone, or 2 or more kinds may be used in combination. In addition, the metal may be a solid solution, an inorganic substance stable to water, or the like.

[ amphiphilic molecule (A) ]

The HLB value of the amphipathic molecule (A) of this embodiment is 1 to 8. It is presumed that if the HLB value of the amphiphilic molecule (A) is in the range of 1 to 8, the amphiphilic molecule (A) exhibits compatibility with the thermoplastic resin (A) based on the lipophilic group, and mainly plays a role of dispersing the inorganic compound (particularly, the metal oxide) in the thermoplastic resin (A). The HLB is an index indicating the balance between hydrophilicity and lipophilicity, and a substance having no hydrophilic group is referred to as hlb=0, a substance having no lipophilic group and only hydrophilic group is referred to as hlb=20, and the range of 0 to 20 is equally divided. The HLB value can be obtained by either a calculation method or an actual measurement method, and in the case of the calculation method, the HLB value can be calculated by the Griffin formula shown below.

HLB＝20×Mw/M

(wherein M is the molecular weight of the amphipathic molecule and Mw is the molecular weight of the hydrophilic portion of the amphipathic molecule.)

The content of the amphiphilic molecule (a) in the masterbatch may be in a range of preferably 0.01 mass% or more, and may be in a range of preferably 40 mass% or less, more preferably 30 mass% or less, and still more preferably 20 mass% or less, based on 100 mass% of the total mass of the thermoplastic resin (a), the inorganic compound, the amphiphilic molecule (a), and the amphiphilic molecule (B). If the content of the amphiphilic molecule (a) is 0.01 mass% or more and 40 mass% or less, the inorganic compound can be made more compatible with the thermoplastic resin (a).

Examples of the amphipathic molecule (a) include the following compounds.

Glycerol fatty acid esters such as glycerol monostearate (HLB value 4.0), self-emulsifying glycerol monostearate (HLB value 6.0), and glycerol monooleate (HLB value 2.5);

polyglyceryl fatty acid esters such as polyglyceryl-6 polyricinoleate (HLB value 3.9), diglycerol monostearate (HLB value 5.0), diglycerol monooleate (HLB value 6.5), diglycerol dioleate (HLB value 7.0), diglycerol monoisostearate (HLB value 5.5), tetraglycerol monostearate (HLB value 6.0), tetraglycerol monooleate (HLB value 6.0), decaglycerol tristearate (HLB value 7.5), decaglycerol trioleate (HLB value 7.0), and decaglycerol pentastearate (HLB value 3.5);

A triisostearate POE (3) glyceride (HLB value 2.0), triisostearate POE (5) glyceride (HLB value 3.0), triisostearate POE (10) glyceride (HLB value 5.0), triisostearate POE (20) glyceride (HLB value 8.0), isostearic POE (3) glyceride (HLB value 6.0), isostearic POE (5) glyceride (HLB value 8.0), isostearic POE (6) glyceride (HLB value 8.0), tristearic POE (3) glyceride (HLB value 2.0), tristearic POE (4) glyceride (HLB value 2.0), tristearic POE (5) glyceride (HLB value 3.0), tristearic POE (6) glyceride (HLB value 3.0), tristearic POE (10) glyceride (HLB value 5.0), tristearic POE (20) glyceride (HLB value 8.0), distearic POE (4) glyceride (HLB value 4.0), trioleatic acid POE (3.0), triolic acid triglyceride (HLB value 3.0) glyceride (HLB value 2.0), triolic acid triglyceride (HLB value 3.0) glyceride (HLB value 5.0;

propylene glycol fatty acid esters such as 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), and propylene glycol monobehenate (HLB value 3.4);

sorbitan fatty acid esters such as sorbitan monopalmitate (HLB value 6.7), sorbitan monostearate (HLB value 4.7), sorbitan sesquistearate (HLB value 4.2), sorbitan tristearate (HLB value 2.1), sorbitan monoisostearate (HLB value 5.0), sorbitan sesquiisostearate (HLB value 4.5), sorbitan monooleate (HLB value 4.3), and sorbitan sesquioleate (HLB value 3.7);

Polyoxyethylene sorbitol fatty acid esters such as POE (6) sorbitol hexastearate (HLB value 3.0);

fatty acid alkanolamides such as palm kernel oil fatty acid dimethanolamide (HLB value 5.5), coconut oil fatty acid diethanolamide (HLB value 5.8), and lauric acid diethanolamide (HLB value 5.8);

polyoxyethylene lanolin/lanolin alcohol/beeswax derivatives such as POE (6) sorbitol beeswax (HLB value 7.5);

polyoxyethylene castor oil/hydrogenated castor oil such as POE (3) castor oil (HLB value 3.0), POE (10) castor oil (HLB value 6.5), POE (5) hydrogenated castor oil (HLB value 6.0), POE (7) hydrogenated castor oil (HLB value 6.0), POE (10) hydrogenated castor oil (HLB value 6.5), POE (40) hydrogenated castor oil (HLB value 12.5);

a POE (3) lauryl ether (HLB value 8.0), a POE (5) lauryl ether (HLB value 1.0), a POE (5) isocetyl ether (HLB value 8.0), a POE (3) cetyl ether (HLB value 6.0), a POE (5) cetyl ether (HLB value 8.0), a POE (2) stearyl ether (HLB value 8.0), a POE (5) stearyl ether (HLB value 8.0), a POE (6) stearyl ether (HLB value 8.0), a POE (5) isostearyl ether (HLB value 8.0), a POE (2) oil ether (HLB value 7.5), a POE (3) oil ether (HLB value 6.0), a POE (5) oil ether (HLB value 8.0), a POE (5) octyl dodecyl ether (HLB value 7.0), a POE (5) behenyl ether (HLB value 7.0), a POE (5) decyl ether (HLB value 6.0), a POE (3.0) alkyl ether (HLB value 8.0), a POE (polyoxyethylene ether (HLB value 7.0), and the like;

POE (2) monostearate (HLB value 4.0), POE (3) monostearate (HLB value 7.0), POE (4) monostearate (HLB value 6.5), POE (5) monostearate (HLB value 8.0), POE (2) monooleate (HLB value 4.5), POE (3) monooleate (HLB value 7.0), POE (6) monooleate (HLB value 8.5), POE (2) distearate (HLB value 2.0), POE (3) distearate (HLB value 3.0), POE (4) distearate (HLB value 4.0), POE (6) distearate (HLB value 5.0), POE (12) distearate (HLB value 8.0), POE (2) distearate (HLB value 3.0), POE (3) distearate (HLB value 3.0), POE (4) distearate (HLB value 4.0), POE (6) distearate (HLB value 6.0), POE (HLB value 3.0), POE (HLB value 3) distearate (HLB value 3.0), POE (2) distearate (HLB value 3), polyoxyethylene fatty acid esters such as POE (3) dioleate (HLB value 3.0), POE (4) dioleate (HLB value 4.0), POE (6) dioleate (HLB value 5.0), POE (8) dioleate (HLB value 6.0), POE (12) dioleate (HLB value 8.0);

polyoxyethylene alkylamines such as POE (2) laurylamine (HLB 5.2), POE (2) stearylamine (HLB 5.1), POE (3) tallow propylenediamine (HLB 5.9), N-bis-N-cyclohexylamine (HLB 4.8), POE (2) m-xylylenediamine (HLB 7.9);

Polyoxyethylene cetyl stearate such as POE (3) cetyl ether stearate (HLB value 3.0), POE (5) cetyl ether stearate (HLB value 4.0), POE (7) cetyl ether stearate (HLB value 6.0), POE (10) cetyl ether stearate (HLB value 7.0);

polyoxyethylene stearyl stearates such as POE (4) stearyl ether stearate (HLB value 4.0), POE (6) stearyl ether stearate (HLB value 5.0), POE (9) stearyl ether stearate (HLB value 6.0), POE (10) stearyl ether stearate (HLB value 7.0), POE (12) stearyl ether stearate (HLB value 8.0);

polyoxyethylene lauryl stearates such as POE (3) lauryl ether stearate (HLB value 3.0), POE (5) lauryl ether stearate (HLB value 5.0), POE (8) lauryl ether stearate (HLB value 7.0), POE (10) lauryl ether stearate (HLB value 8.0);

POE (5) hydrogenated castor oil isostearate (HLB value 4.0), POE (10) hydrogenated castor oil isostearate (HLB value 5.0), POE (15) hydrogenated castor oil isostearate (HLB value 7.0), POE (20) hydrogenated castor oil isostearate (HLB value 8.0), POE (5) hydrogenated castor oil triisostearate (HLB value 2.0), POE (10) hydrogenated castor oil triisostearate (HLB value 4.0), POE (15) hydrogenated castor oil triisostearate (HLB value 5.0), POE (20) hydrogenated castor oil triisostearate (HLB value 6.0), POE (30) hydrogenated castor oil triisostearate (HLB value 7.0), POE (40) hydrogenated castor oil triisostearate (HLB value 8.0), POE (20) hydrogenated castor oil laurate (HLB value 8.0) and the like;

Polyoxyethylene trimethylolpropane fatty acid esters such as POE (3) trimethylolpropane tristearate (HLB value 2.0), POE (5) trimethylolpropane tristearate (HLB value 3.0), POE (10) trimethylolpropane tristearate (HLB value 5.0), POE (3) trimethylolpropane trimyristate (HLB value 2.0), POE (5) trimethylolpropane trimyristate (HLB value 3.0), POE (3) trimethylolpropane distearate (HLB value 3.0), POE (4) trimethylolpropane distearate (HLB value 4.0), POE (5) trimethylolpropane distearate (HLB value 4.0), POE (3) trimethylolpropane triisostearate (HLB value 2.0), POE (20) trimethylolpropane triisostearate (HLB value 8.0) and the like.

In addition, 1 kind selected from these amphiphilic molecules (a) may be used alone, or 2 or more kinds may be used in combination.

Among the above amphiphilic molecules (a), from the viewpoint of high heat resistance, 1 or 2 selected from the group consisting of polyglycerin fatty acid esters and fatty acid alkanolamides are preferable, and polyglycerin fatty acid esters are more preferable.

[ amphiphilic molecule (B) ]

The HLB value of the amphipathic molecule (B) of this embodiment is 10 to 18. It is presumed that when the HLB value of the amphiphilic molecule (B) is in the range of 10 to 18, the amphiphilic molecule (B) exhibits adsorptivity with an inorganic compound (particularly, a metal oxide) based on a hydrophilic group, and mainly plays a role of stabilizing dispersion of the inorganic compound in the thermoplastic resin (A).

The content of the amphiphilic molecule (B) in the master batch may be in a range of preferably 0.01 mass% or more, and may be in a range of preferably 40 mass% or less, more preferably 30 mass% or less, and still more preferably 20 mass% or less, based on 100 mass% of the total mass of the thermoplastic resin (a), the inorganic compound, the amphiphilic molecule (a), and the amphiphilic molecule (B). If the content of the amphiphilic molecule (B) is 0.01 mass% or more and 40 mass% or less, the dispersion of the inorganic compound in the thermoplastic resin (a) can be more stable.

Examples of the amphiphilic molecule (B) include the following compounds.

Polyglycerides such as hexaglyceride monolaurate (HLB value 14.5), hexaglyceride monomyristate (HLB value 11.0), decaglyceride monolaurate (HLB value 15.5), decaglyceride monomyristate (HLB value 14.0), decaglyceride monostearate (HLB value 12.0), decaglyceride monoisostearate (HLB value 12.0), decaglyceride monooleate (HLB value 12.0), and decaglyceride diisostearate (HLB value 10.0);

a glycerol monostearate POE (15) (HLB value 13.5), a glycerol monooleate POE (15) (HLB value 14.5), a glycerol triisostearate POE (30) (HLB value 10.0), a glycerol triisostearate POE (40) (HLB value 11.0), a glycerol triisostearate POE (50) (HLB value 12.0), a glycerol triisostearate POE (60) (HLB value 13.0), a glycerol isostearate POE (8) (HLB value 10.0), a glycerol isostearate POE (10) (HLB value 10.0), a glycerol isostearate POE (15) (HLB value 12.0), a glycerol isostearate POE (20) (HLB value 13.0), a glycerol isostearate POE (25) (HLB value 14.0), a glycerol isostearate POE (30) (HLB value 15.0), a glycerol isostearate POE (40) (HLB value 15.0), a glycerol isostearate POE (50) (HLB value 16.0), a glycerol isostearate POE (60) (HLB value 16.0), a glycerol trioleate (HLB value 12.0) (HLB value 0), a glycerol trioleate (HLB value 12.0), and the like;

Polyoxyethylene sorbitan fatty acid esters such as POE (20) sorbitan mono-coconut oil fatty acid ester (HLB value 16.9), POE (20) sorbitan monopalmitate (HLB value 15.6), POE (20) sorbitan monostearate (HLB value 14.9), POE (20) sorbitan tristearate (HLB value 10.5), POE (20) sorbitan monoisostearate (HLB value 15.0), POE (20) sorbitan monooleate (HLB value 15.0), POE (6) sorbitan monooleate (HLB value 10.0), POE (20) sorbitan trioleate (HLB value 11.0);

polyoxyethylene sorbitol fatty acid esters such as POE (6) sorbitol monolaurate (HLB value 15.5), POE (60) sorbitol tetrastearate (HLB value 13.0), POE (30) sorbitol tetraoleate (HLB value 10.5), POE (40) sorbitol tetraoleate (HLB value 12.5), and POE (60) sorbitol tetraoleate (HLB value 14.0);

polyoxyethylene lanolin/lanolin alcohol/beeswax derivatives such as POE (10) lanolin (HLB value 12.0), POE (20) lanolin (HLB value 13.0), POE (30) lanolin (HLB value 15.0), POE (5) lanolin alcohol (HLB value 12.5), POE (10) lanolin alcohol (HLB value 15.5), POE (20) lanolin alcohol (HLB value 16.0), POE (40) lanolin alcohol (HLB value 17.0);

polyoxyethylene castor oil such as POE (20) castor oil (HLB value 10.5), POE (40) castor oil (HLB value 12.5), POE (50) castor oil (HLB value 14.0), POE (60) castor oil (HLB value 14.0), POE (20) hydrogenated castor oil (HLB value 10.5), POE (30) hydrogenated castor oil (HLB value 11.0), POE (40) hydrogenated castor oil (HLB value 12.5), POE (50) hydrogenated castor oil (HLB value 13.5), POE (60) hydrogenated castor oil (HLB value 14.0), POE (80) hydrogenated castor oil (HLB value 15.0), POE (100) hydrogenated castor oil (HLB value 16.5);

Polyoxyethylene sterols/hydrogenated sterols such as POE (10) phytosterols (HLB 12.5), POE (20) phytosterols (HLB 15.5), POE (30) phytosterols (HLB 18.0), POE (25) phytostanols (HLB 14.5), POE (30) cholestanol (HLB 17.0);

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) isocetyl ether (HLB value 11.0), POE (15) isocetyl ether (HLB value 13.0), POE (20) isocetyl ether (HLB value 14.0) POE (25) isocetyl ether (HLB value 15.0), POE (5.5) hexadecyl ether (HLB value 10.5), POE (7) hexadecyl ether (HLB value 11.5), POE (10) hexadecyl ether (HLB value 13.5), POE (12) hexadecyl ether (HLB value 12.0), POE (15) hexadecyl ether (HLB value 15.5), POE (17) hexadecyl ether (HLB value 13.0), POE (20) hexadecyl ether (HLB value 17.0), POE (23) hexadecyl ether (HLB value 18.0), POE (8) stearyl ether (HLB value 10.0), POE (11) stearyl ether (HLB value 11.0), A stearyl ether (HLB value of 12.0) of POE (15), a stearyl ether (HLB value of 18.0) of POE (20), a stearyl ether (25) of (HLB value of 14.0), a stearyl ether (30) of (HLB value of 15.0), a stearyl ether (40) of (HLB value of 16.0), an isostearyl ether (10) of (HLB value of 11.0), an isostearyl ether (15) of (HLB value of 12.0), an isostearyl ether (20) of (POE) of (20) of (HLB value of 13.0), an isostearyl ether (HLB value of 14.0) of (25), an oil ether (3) of (HLB value of 6.0), an oil ether (7) of (HLB value of 10.5), an oil ether (8) of (HLB value of 10.0) POE (10) oil ether (HLB value 14.5), POE (12) oil ether (HLB value 11.0), POE (15) oil ether (HLB value 16.0), POE (20) oil ether (HLB value 17.0), POE (23) oil ether (HLB value 14.0), POE (50) oil ether (HLB value 18.0), POE (10) octyldodecyl ether (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), behenyl ether (HLB 10.0), behenyl ether (HLB 16.5) and POE (20), behenyl ether (HLB 18.0), decyl tetradecyl ether (HLB 11.0) and POE (15), decyl tetradecyl ether (HLB 12.0) and POE (25), decyl tetradecyl ether (HLB 13.0), alkyl ether (C12-15) and (HLB 10.5) and POE (8) (C9-11) and (HLB 13.9) and alkyl ether (C12-15) and (HLB 15.5) and secondary alkyl ether (HLB 10.5) and POE (7) and cholesterol ether (HLB 12.0) and cholesterol ether (HLB 10.0) and cholesterol ether (POE 11.0) and cholesterol ether (HLB 12.0) and cholesterol ether (C12-15) and cholesterol ether (HLB 14.0) and the like;

Polyoxyethylene polyoxypropylene ethers such as POE (10) POP (4) cetyl ether (HLB value 10.5), POE (20) POP (4) cetyl ether (HLB value 16.5), POE (20) POP (8) cetyl ether (HLB value 12.5), POE (20) POP (6) tetradecyl ether (HLB value 11.0), POE (30) POP (6) tetradecyl ether (HLB value 12.0), POE (7) POP (2) tetradecyl ether (HLB value 10.0), POE (10) POP (2) tetradecyl ether (HLB value 12.0), POE (12) POP (2) tetradecyl ether (HLB value 12.0), POE (15) POP (2) tetradecyl ether (HLB value 13.0), POE (20) POP (2) tetradecyl ether (HLB value 14.0), POE (30) POP (2) tetradecyl ether (HLB value 15.0);

POE (10) monolaurate (HLB value 12.5), POE (12) monolaurate (HLB value 14.0), POE (10) monostearate (HLB value 11.0), POE (20) monostearate (HLB value 14.0), POE (25) monostearate (HLB value 15.0), POE (30) monostearate (HLB value 15.0), POE (40) monostearate (HLB value 17.5), POE (45) monostearate (HLB value 18.0), POE (55) monostearate (HLB value 18.0), POE (15) monostearate (HLB value 18.0), POE (10) monooleate (HLB value 11.0), POE (150) distearate (HLB value 16.5), POE (8) isostearate (HLB value 10.0), POE (10) isostearate (HLB value 11.0), POE (12) isostearate (HLB value 12.0), POE (20) isostearate (HLB value 14.0), POE (polyoxyethylene (POE) distearate (HLB value 12.0), and the like;

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) vinyltallow amine (HLB value 11.0), POE (8) vinyltallow amine (HLB value 11.9), POE (10) vinyltallow amine (HLB value 12.7), POE (13.5) vinyltallow amine (HLB value 11.0), POE (20) vinyltallow amine (HLB value 15.5), POE (30) vinyltallow amine (HLB value 16.7) polyoxyethylene alkylamines such as POE (40) ethylene tallow amine (HLB value 17.4), POE (7) stearyl amine (HLB value 10.7), POE (10) stearyl amine (HLB value 12.8), POE (15) stearyl amine (HLB value 14.3), POE (20) stearyl amine (HLB value 115.3), POE (30) stearyl amine (HLB value 16.7), POE (45) stearyl amine (HLB value 17.6), POE (15) tallow propylenediamine (HLB value 13.4), POE (50) stearyl propylenediamine (HLB value 17.4), POE (4) m-xylylenediamine (HLB value 11.3)

Polyoxyethylene alkylamides such as POE (50) stearylamide (HLB value 17.8)

Polyoxyethylene glyceryl monostearate such as POE (10) glyceride (HLB value 11.0), POE (15) glyceride (HLB value 13.0), POE (20) glyceride (HLB value 14.0), POE (30) glyceride (HLB value 15.0), and POE (40) glyceride (HLB value 16.0);

POE hydrogenated castor oil fatty acid esters such as POE (40) hydrogenated castor oil isostearate (HLB value 11.0), POE (50) hydrogenated castor oil isostearate (HLB value 12.0), POE (58) hydrogenated castor oil isostearate (HLB value 12.0), POE (60) hydrogenated castor oil triisostearate (HLB value 10.0), POE (30) hydrogenated castor oil laurate (HLB value 10.0), POE (40) hydrogenated castor oil laurate (HLB value 11.0), POE (50) hydrogenated castor oil laurate (HLB value 12.0), POE (60) hydrogenated castor oil laurate (HLB value 13.0);

polyoxyethylene trimethylolpropane fatty acid esters such as POE (30) trimethylolpropane trimyristate (HLB value 11.0), POE (30) trimethylolpropane triisostearate (HLB value 10.0), POE (40) trimethylolpropane triisostearate (HLB value 11.0), POE (50) trimethylolpropane triisostearate (HLB value 12.0);

sucrose fatty acid esters such as sucrose laurate monoester (HLB value 16.0), sucrose myristate monoester (HLB value 16.0), sucrose palmitate monoester (HLB value 16.0), sucrose stearate monoester (HLB value 16.0), and sucrose oleate monoester (HLB value 16.0).

In addition, 1 kind selected from these amphiphilic molecules (B) may be used alone, or 2 or more kinds may be used in combination.

Among the above amphiphilic molecules (B), from the viewpoint of high heat resistance, 1 or 2 selected from polyoxyethylene sorbitol fatty acid esters and polyoxyethylene alkyl ethers are preferable, and polyoxyethylene alkyl ethers are more preferable.

For example, if "POE (8) (C9-11) alkyl ether" is described, "POE" means polyoxyethylene, "(8)" means m in the following formula (2), and "alkyl (C9-11) alkyl" means an alkyl mixture having 9 to 11 carbon atoms.

R-(CH ₂ CH ₂ O) _m -H···(2)

[ amphipathic molecule (A) and amphipathic molecule (B) ]

The mass ratio of the amphiphilic molecule (a) to the amphiphilic molecule (B) in the master batch is preferably the amphiphilic molecule (a): amphiphilic molecule (B) =10 to 90:90 to 10. Thus, both the effect of compatibilizing the inorganic compound with the thermoplastic resin (a) and the effect of stabilizing the dispersion of the inorganic compound in the thermoplastic resin (a) can be well-balanced.

[ other Components ]

The master batch may contain other components than the thermoplastic resin (a), the inorganic compound, the amphiphilic molecule (a), and the amphiphilic molecule (B) within a range not departing from the gist of the function.

The other components include, specifically, antioxidants, ultraviolet absorbers, colorants, pigments, dyes, foaming agents, lubricants, flame retardants, fillers, and the like.

Thermoplastic resin composition and molded article

The thermoplastic resin composition and the molded article of the present embodiment are obtained by blending a masterbatch with the thermoplastic resin (B). The thermoplastic resin composition or the molded article is a cured product obtained by mixing the master batch and the thermoplastic resin (B) (which is obtained by softening and flowing by heating and curing by cooling). The thermoplastic resin composition is not particularly limited, and for example, an intermediate molded product when a thermoplastic resin molded product is obtained from a master batch is a material having a predetermined form such as a pellet form or a powder form.

[ thermoplastic resin (B) ]

The content of the masterbatch may be in the range of preferably 1 mass% or more, and may be in the range of preferably 90 mass% or less, more preferably 80 mass% or less, and still more preferably 70 mass% or less, when the total mass of the masterbatch and the thermoplastic resin (B) in the thermoplastic resin composition or the molded article is 100 mass%.

The thermoplastic resin (B) is not particularly limited, and examples thereof include polyolefin resins such as polyethylene, polypropylene, poly (4-methyl-1-pentene) and poly (1-butene); polyester resins such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate; polyamide resins such as polyamide-6 (nylon-6), polyamide-66 (nylon-66) and poly (m-xylylenediamine) adipamide; ethylene/unsaturated ester copolymers such as ethylene/vinyl ester copolymers and ethylene/unsaturated carboxylic acid ester copolymers; ethylene/unsaturated carboxylic acid-based copolymer or ionomer resin thereof; poly (meth) acrylic resins such as poly (meth) acrylate resins; chlorine-based resins such as polyvinyl chloride and polyvinylidene chloride; fluorine-based resins such as polytetrafluoroethylene, ethylene tetrafluoroethylene copolymer, polyvinylidene fluoride and polyvinylidene fluoride; a polystyrene resin; polyether-based resins such as polyether-ether-ketone resins and polyether-ketone resins; a polycarbonate resin; polyphenylene resins such as polyphenylene ether resins and polyphenylene sulfide resins; a polyvinyl acetate resin; a polyacrylonitrile resin; thermoplastic elastomers, and the like. In addition, it is possible to use 1 kind selected from these thermoplastic resins alone, or to use 2 kinds or more in combination.

When classified by density or shape, high Density Polyethylene (HDPE), low Density Polyethylene (LDPE), ultra low density polyethylene (VLDPE), linear Low Density Polyethylene (LLDPE), ultra high molecular weight polyethylene (UHMW-PE), and among them, low density polyethylene and linear low density polyethylene are preferable.

From the viewpoint of molding filaments and films, the thermoplastic resin (B) preferably contains 1 or 2 or more kinds selected from polyethylene terephthalate, polyamide 6, polypropylene, linear low density polyethylene and polycarbonate.

The thermoplastic resin (B) in the thermoplastic resin composition or the molded article may be the same as the thermoplastic resin (a) or may be different from the thermoplastic resin (a), and from the viewpoint of compatibility, the same type of resin is preferably used.

[ amphiphilic molecule (A) ]

The content of the amphiphilic molecule (a) may be in the range of preferably 0.01 mass% or more, and may be in the range of preferably 40 mass% or less, more preferably 30 mass% or less, and still more preferably 20 mass% or less, based on 100 mass% of the total mass of the master batch and the thermoplastic resin (B) in the thermoplastic resin composition or the molded article.

[ amphiphilic molecule (B) ]

The content of the amphiphilic molecule (B) may be in the range of preferably 0.01 mass% or more, and may be in the range of preferably 40 mass% or less, more preferably 30 mass% or less, and still more preferably 20 mass% or less, when the total mass of the master batch and the thermoplastic resin (B) in the thermoplastic resin composition or the molded article is 100 mass%.

[ other Components ]

The thermoplastic resin composition or the molded article may contain other components than the thermoplastic resin (a), the inorganic compound, the amphiphilic molecule (a) and the amphiphilic molecule (B) as long as the functions thereof do not depart.

The thermoplastic resin molded article is not limited in its form, and may be any one selected from filaments (long fibers), short fibers (staple), nonwoven fabrics, and hollow fibers, for example. The filaments may be multifilament twisted from several tens of filaments (monofilaments), or may be monofilaments. The yarn breakage during spinning can be suppressed. In addition, the thermoplastic resin molded body may be a film. In particular, in the case of a thermoplastic resin molded article, for example, a filament having a fiber diameter of 100 μm or less or a film having a thickness of 100 μm or less, secondary aggregation of an inorganic compound can be prevented, and the processability, mechanical properties, and appearance quality of the molded article can be improved.

< method for producing master batch >

The method for producing a master batch according to the present embodiment includes the steps of: a step (I) of mixing an inorganic compound containing a metal oxide as a main component, an amphipathic molecule (A) having an HLB value in the range of 1 to 8, and an amphipathic molecule (B) having an HLB value in the range of 10 to 18, and preparing an aqueous dispersion containing 1 to 80 parts by mass of the inorganic compound; and (II) supplying the aqueous dispersion in an amount of 1 to 300 parts by mass based on 100 parts by mass of the thermoplastic resin (A) and melt-mixing the aqueous dispersion.

The content of the inorganic compound in the aqueous dispersion used in the step (I) may be in a range of 1 mass% or more and 80 mass% or less, preferably 1 mass% or more and 70 mass% or less, more preferably 1 mass% or more and 60 mass% or less, with the total mass of the inorganic compound, the amphiphilic molecule (a), the amphiphilic molecule (B) and water being 100 mass%. If the content of the inorganic compound is less than 1 mass%, it is difficult to obtain desired properties based on the inorganic compound in the thermoplastic resin composition or the molded article, and if it exceeds 80 mass%, it is difficult to obtain high dispersion of the inorganic compound, and further, it is easy to obtain a decrease in mechanical properties and poor appearance. Thus, the content of the inorganic compound in the aqueous dispersion is set to a value within the above range.

The content of the amphiphilic molecule (a) in the aqueous dispersion may be in a range of preferably 0.01 mass% or more, and may be in a range of preferably 40 mass% or less, more preferably 30 mass% or less, and still more preferably 20 mass% or less, where the total mass of the inorganic compound, the amphiphilic molecule (a), the amphiphilic molecule (B), and water in the aqueous dispersion is 100 mass%. If the content of the amphiphilic molecule (a) is 0.01 mass% or more and 20 mass% or less, the inorganic compound can be made more compatible with the thermoplastic resin (a).

The content of the amphiphilic molecule (B) in the aqueous dispersion may be in a range of preferably 0.01 mass% or more, and may be in a range of preferably 40 mass% or less, more preferably 30 mass% or less, and still more preferably 20 mass% or less, where the total mass of the inorganic compound, the amphiphilic molecule (a), the amphiphilic molecule (B), and water in the aqueous dispersion is 100 mass%. If the content of the amphiphilic molecule (B) is 0.01 mass% or more and 40 mass% or less, the dispersion of the inorganic compound in the thermoplastic resin (a) can be more stable.

In the step (I), an aqueous dispersion may be prepared by further mixing an inorganic compound containing a metal oxide as a main component, an amphipathic molecule (a) having an HLB value in the range of 1 to 8, and an amphipathic molecule (B) having an HLB value in the range of 10 to 18.

In this case, the content of the inorganic compound in the aqueous dispersion used in the step (I) may be preferably 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, with the total mass of the inorganic compound, the amphiphilic molecule (a), the amphiphilic molecule (B), the water-soluble alcohol, and the water being 100% by mass. If the content of the inorganic compound is less than 1 mass%, it becomes difficult to obtain desired properties based on the inorganic compound in the thermoplastic resin composition or the molded article, and if it exceeds 80 mass%, it becomes difficult to obtain high dispersion of the inorganic compound, and further, it becomes easy to cause deterioration of mechanical properties and appearance defects. Thus, the content of the inorganic compound in the aqueous dispersion is set to a value within the above range.

The content of the amphiphilic molecule (a) in the aqueous dispersion may be in a range of preferably 0.01 mass% or more, and may be in a range of preferably 40 mass% or less, more preferably 30 mass% or less, and still more preferably 20 mass% or less, based on 100 mass% of the total mass of the inorganic compound, the amphiphilic molecule (a), the amphiphilic molecule (B), the water-soluble alcohol, and the water. If the content of the amphiphilic molecule (a) is 0.01 mass% or more and 40 mass% or less, the inorganic compound can be made more compatible with the thermoplastic resin (a).

The content of the amphiphilic molecule (B) in the aqueous dispersion may be in a range of preferably 0.01 mass% or more, and may be in a range of preferably 40 mass% or less, more preferably 30 mass% or less, and still more preferably 20 mass% or less, based on 100 mass% of the total mass of the inorganic compound, the amphiphilic molecule (a), the amphiphilic molecule (B), the water-soluble alcohol, and the water. If the content of the amphiphilic molecule (B) is 0.01 mass% or more and 40 mass% or less, the dispersion of the inorganic compound in the thermoplastic resin (a) can be more stable.

The content of the water-soluble alcohol in the aqueous dispersion may be in a range of preferably 0.01 mass% or more, and may be in a range of preferably 40 mass% or less, more preferably 30 mass% or less, and still more preferably 20 mass% or less, where the total mass of the inorganic compound, the amphiphilic molecule (a), the amphiphilic molecule (B), the water-soluble alcohol, and the water in the aqueous dispersion is 100 mass%. The content of the water-soluble alcohol is 0.01 mass% or more and 40 mass% or less, whereby the stability of the system can be improved.

[ other Components ]

The aqueous dispersion may contain other components than the above-described inorganic compound, amphiphilic molecule (a), amphiphilic molecule (B) and water-soluble alcohol within a range not departing from the gist of its function. The other components include, specifically, antioxidants, ultraviolet absorbers, colorants, pigments, dyes, foaming agents, lubricants, flame retardants, fillers, and the like.

In the step (II), the aqueous dispersion prepared in the step (I) is supplied in an amount of 1 to 300 parts by mass based on 100 parts by mass of the thermoplastic resin (a) and melt-mixed to obtain a master batch. The amount of the aqueous dispersion to be supplied to the thermoplastic resin (a) may be preferably in the range of 1 part by mass or more and 200 parts by mass or less. If the amount of the aqueous dispersion to be supplied is more than 300 parts by mass, injection into a device for melt mixing becomes difficult, and it becomes difficult to raise the temperature to the melting temperature of the thermoplastic resin (a), and melt mixing becomes difficult. On the other hand, if the amount of the aqueous dispersion to be supplied is 1 part by mass or more and 300 parts by mass or less relative to the thermoplastic resin (a), secondary aggregation of the inorganic compound during dehydration drying of melt mixing can be prevented, and the metal oxide can be uniformly dispersed in the master batch. Thus, the amount of the aqueous dispersion to be supplied is set to a value within the above range.

In melt mixing, a kneading machine such as an extruder (single screw extruder, twin screw extruder), kneader, banbury mixer, or the like can be used, and a kneading extruder is preferable in that kneading can be continuously performed.

The heating temperature in the melt mixing step may be determined according to the easiness of melting the thermoplastic resin as the matrix resin, and may be in the range of preferably 100 ℃ or higher, more preferably 120 ℃ or higher, still more preferably 150 ℃ or higher, and may be in the range of preferably 400 ℃ or lower, more preferably 380 ℃ or lower, still more preferably 350 ℃ or lower. When the heating temperature is 100 ℃ or higher, the thermoplastic resin is easily melted, and the inorganic compound is easily dispersed in the thermoplastic resin, and when the heating temperature is 400 ℃ or lower, thermal degradation of each component can be suppressed.

In the step (II), an aqueous dispersion containing a water-soluble alcohol may be used. In this case, the aqueous dispersion prepared in the supplying step (I) may be 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, still more preferably 1 part by mass or more and 150 parts by mass or less with respect to 100 parts by mass of the thermoplastic resin (a) and melt-mixed. By using an aqueous dispersion containing a water-soluble alcohol, the dispersion of the inorganic compound in the thermoplastic resin (a) can be made more stable.

After melt mixing, the mixture may be molded or processed into a shape (e.g., pellet shape) that meets the intended use of the masterbatch.

When the master batch is formed into pellets, the master batch is melt kneaded to form strands, and the strands are cut by a pelletizer to form pellets. The pellet-shaped master batch can be used as a material for further molding, and for example, can be used as a thermoplastic resin composition or a material for molded articles. The pellet-shaped master batch may be molded by a molding machine (for example, an injection molding machine, an extrusion molding machine, or the like).

Thermoplastic resin composition and method for producing molded article

The method for producing the thermoplastic resin composition or the molded article of the present embodiment comprises the following steps: the master batch obtained by the above-described production method is melt-mixed with the thermoplastic resin (B). Thus, the thermoplastic resin molded article can be obtained as it is, but the target thermoplastic resin molded article can also be obtained by once passing through a step of obtaining a granular or powdery thermoplastic resin composition and then passing through a step of melt-molding the obtained granular or powdery thermoplastic resin composition. By obtaining the thermoplastic resin molded article through the masterbatch in this manner, the inorganic compound can be stably and uniformly dispersed in the thermoplastic resin molded article, and the desired functions and properties due to the inorganic compound can be sufficiently imparted to the thermoplastic resin molded article.

The masterbatch and the thermoplastic resin (B) are preferably melt-mixed so that the content of the masterbatch is preferably 1 mass% or more and 90 mass% or less, more preferably 1 mass% or more and 80 mass% or less, and still more preferably 1 mass% or more and 70 mass% or less, based on 100 mass% of the total mass of the masterbatch and the thermoplastic resin (B). If the content of the masterbatch is 1 mass% or more and 90 mass% or less, the inorganic compound can be dispersed more stably and uniformly.

In the melt mixing step, other components than the master batch and the thermoplastic resin (B) may be further mixed. For example, in the mixing step, an antioxidant may be mixed together with the master batch and the thermoplastic resin (B).

After melt mixing, the thermoplastic resin can be molded or processed into a shape (for example, a thread shape, a nonwoven fabric shape, or a film shape) suitable for the purpose of use of the thermoplastic resin molded article.

When the thermoplastic resin molded body is formed into filaments (filaments, short fibers, hollow filaments), the filaments can be formed by melt-kneading and then discharging the molten resin from one or more holes having a predetermined cross-sectional shape. The filament-shaped thermoplastic resin molded article may be molded by further post-treatment such as stretching, heat treatment, twisting, etc., or may be mixed with other filaments and spun to form a mixed yarn or mixed filament.

When the thermoplastic resin molded body is formed into a nonwoven fabric, the fibers formed from the molten resin are collected on a net after melt kneading, whereby the nonwoven fabric can be formed. The nonwoven fabric-like thermoplastic resin molded article can be further molded by a post-treatment such as bonding the fibers of the binder to each other and applying an external force thereto, and interlacing the fibers.

When the thermoplastic resin molded body is formed into a film shape, the molten resin is discharged (extruded) from the slit-shaped holes after melt kneading, whereby the film shape can be formed. The film-like thermoplastic resin molded body may be molded by a press molding method or a vacuum molding method, or may be formed on a base layer to form a multilayer film.

Examples

Hereinafter, examples of the present invention will be described. The present invention is not limited to the examples shown below. In the examples, "parts" means mass parts unless otherwise specified.

Example 1

(production of aqueous Dispersion)

To 30 parts by mass of titanium oxide particles (ST-21, average particle diameter 20nm, manufactured by Shiniter Co., ltd.), 1 part by mass of polyglycerin fatty acid ester (SY Glyster CRS75, HLB3.5, manufactured by Sakaki Co., ltd.), 1 part by mass of polyoxyethylene alkyl ether (SAFETYCU LI-3085, HLB value 13.9, manufactured by green wood oil Co., ltd.), and 1 part by mass of ethanol, which is a water-soluble alcohol, 67 parts by mass of water was added, and a homogenizer was used to obtain an aqueous dispersion (1).

(production of master batch)

100 parts by mass of polypropylene (Prime Polymer Co., ltd., "Y-2000 GV") was melt-kneaded in a 30mm phi twin-screw vented extruder (set temperature 230 ℃ C., screen filter having a particle diameter of 40 μm), and 30 parts by mass of an aqueous dispersion (1) was injected from a liquid-adding nozzle from the upstream part of the extruder, and water was evaporated from a vent and melt-kneaded. The obtained thermoplastic resin composition was pelletized to obtain a master batch (1).

(production of filaments)

10 parts by mass of a master batch (1) was mixed with 90 parts by mass of polypropylene (Prime Polymer Co., ltd., "Y-2000 GV"), vacuum dried at 150℃for 12 hours, and then melt-spun at a spinning temperature of 230℃by a spinning machine, and drawn 3 times to obtain a filament (1) of 3dtex (fiber diameter about 15 μm).

Example 2

(production of aqueous Dispersion)

An aqueous dispersion (2) was obtained in the same manner as in example 1 except that the amphipathic molecule was changed to a polyglycerin fatty acid ester (SY glster CRS75, manufactured by sakagu pharmaceutical industry, HLB value 3.5) and a polyoxyethylene sorbitol fatty acid ester (RHEODOL 430V, manufactured by hewang corporation, HLB value 10.5).

(production of master batch)

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).

(production of filaments)

A filament (2) was obtained in the same manner as in example 1, except that the master batch (1) was changed to the master batch (2).

Example 3

(production of aqueous Dispersion)

An aqueous dispersion (3) was obtained in the same manner as in example 1 except that the amphipathic molecule was changed to an alkyl alkanolamide (AMINON PK-02S, HLB value 5.5, manufactured by Kagaku corporation) and a polyoxyethylene alkyl ether (SAFETYCUT LI-3085, HLB value 13.9, manufactured by green wood oil industry Co., ltd.).

(production of master batch)

A master batch (3) was obtained in the same manner as in example 1 except that the aqueous dispersion (1) was changed to the aqueous dispersion (3).

(production of filaments)

A filament (3) was obtained in the same manner as in example 1, except that the master batch (1) was changed to the master batch (3).

Example 4

(production of aqueous Dispersion)

An aqueous dispersion (4) was obtained in the same manner as in example 1 except that the amphipathic molecule was changed to an alkyl alkanolamide (amion PK-02S, manufactured by king corporation, HLB value 5.5) and a polyglycerin fatty acid ester (RHEODOL 430V, manufactured by king corporation, HLB value 10.5).

(production of master batch)

A master batch (4) was obtained in the same manner as in example 1 except that the aqueous dispersion (1) was changed to the aqueous dispersion (4).

(production of filaments)

A filament (4) was obtained in the same manner as in example 1, except that the master batch (1) was changed to the master batch (4).

Example 5

(production of aqueous Dispersion)

An aqueous dispersion (5) was obtained in the same manner as in example 1 except that the titanium oxide particles were changed to silicon oxide particles (QSG-30, manufactured by Xinyue chemical Co., ltd., and the average particle diameter was 30 nm).

(production of master batch)

A master batch (5) was obtained in the same manner as in example 1 except that the aqueous dispersion (1) was changed to the aqueous dispersion (5).

(production of filaments)

A filament (5) was obtained in the same manner as in example 1, except that the master batch (1) was changed to the master batch (5).

Example 6

(production of aqueous Dispersion)

An aqueous dispersion (6) was obtained in the same manner as in example 1 except that the titanium oxide particles were changed to zinc oxide particles (FINEX-30, manufactured by Sakai chemical Co., ltd., average particle diameter: 35 nm).

(production of master batch)

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 (6).

(production of filaments)

A filament (6) was obtained in the same manner as in example 1, except that the master batch (1) was changed to the master batch (6).

Example 7

(production of master batch)

A masterbatch (7) was obtained in the same manner as in example 1 except that the polypropylene was changed to high-density polyethylene (Novatec HY430, mitsubishi chemical Co., ltd.) and the extrusion temperature was changed to 200 ℃.

(production of filaments)

10 parts by mass of a master batch (7) was mixed with 90 parts by mass of a high-density polyethylene modified with polypropylene (Novatec HY430, mitsubishi chemical corporation), and then melt-spun at a spinning temperature of 200℃by a spinning machine to obtain a 3dtex filament (7) by 3-fold drawing.

Example 8

(production of master batch)

A masterbatch (8) was obtained in the same manner as in example 1 except that polypropylene was changed to polyethylene terephthalate (UNITIKA ltd. MA-2101M ", manufactured by uniika ltd. And the Intrinsic Viscosity (IV) was 0.63) and the extrusion temperature was changed to 280 ℃.

(production of filaments)

10 parts by mass of a master batch (8) was mixed with 90 parts by mass of polyethylene terephthalate modified with polypropylene (UNITKA LTD. Product "SA-1206", intrinsic Viscosity (IV) 1.07), vacuum-dried at 150℃for 12 hours, and then melt-spun at a spinning temperature of 290℃by a spinning machine to obtain a 3dtex filament (8) by 3-fold stretching.

Example 9

(production of master batch)

A masterbatch (9) was obtained in the same manner as in example 1 except that the polypropylene was changed to polyamide-6 (UBE Nylon (registered trademark) 1013B, manufactured by yu xing corporation) and the extrusion temperature was changed to 260 ℃.

(production of filaments)

10 parts by mass of a master batch (9) was mixed with 90 parts by mass of polyamide-6 (UBE Nylon (registered trademark) 1018I, manufactured by Yu Xing Co., ltd.) and dried at 110℃for 12 hours under vacuum, and then melt-spun at 260℃with a spinning machine to obtain a 3dtex filament (9) by 3-fold drawing.

Example 10

(production of master batch)

A master batch (10) was obtained in the same manner as in example 1 except that the polypropylene was changed to polycarbonate (Mitsubishi Engineering-Plastics Corporation, "Lupilon S-3000"), and the extrusion temperature was changed to 280 ℃.

(production of filaments)

10 parts by mass of a master batch (10) was mixed with 90 parts by mass of a polycarbonate (Mitsubishi Engineering-Plastics Corporation "Lupilon S-3000"), and then melt-spun at a spinning temperature of 300℃by a spinning machine to obtain a 3dtex filament (10) by 2-fold drawing.

Example 11

(production of film)

10 parts by mass of the master batch (1) was mixed with 90 parts by mass of polypropylene (Prime Polymer Co., ltd., "Y-2000 GV"), and then melt-molded at a film-forming temperature of 230℃by using a 20mm single screw extruder connected with a 100mm wide T die, to obtain a film (1) having a thickness of 10. Mu.m.

Comparative example 1

(production of masterbatch and filament)

An aqueous dispersion (7), a masterbatch (11) and filaments (11) were obtained in the same manner as in example 1 except that only alkylalkanolamide (amion PK-02S, manufactured by Kagaku corporation, HLB value 5.5) was used as the amphiphilic molecule.

Comparative example 2

(production of masterbatch and filament)

An aqueous dispersion (8), a masterbatch (12) and filaments (12) were obtained in the same manner as in example 1, except that only polyglycerin fatty acid ester (RHEODOL 430V, manufactured by Kabushiki Kaisha, HLB value 10.5) was used as the amphipathic molecule.

Comparative example 3

An aqueous dispersion (9), a masterbatch (13) and a filament (13) were obtained in the same manner as in example 1, except that an alkyl alkanolamide (amion PK-02S, manufactured by king corporation, HLB value 5.5) and a sorbitan fatty acid ester (RHEODOL SP-L10, manufactured by king corporation, HLB value 8.6) were used as amphiphilic molecules.

Comparative example 4

An aqueous dispersion (10), a masterbatch (14) and filaments (14) were obtained in the same manner as in example 1, except that a sorbitan fatty acid ester (RHEODOL SP-L10, manufactured by Kabushiki Kaisha, HLB value 8.6) and a polyglycerin fatty acid ester (RHEODOL 430V, manufactured by Kaisha, HLB value 10.5) were used as amphiphilic molecules.

Comparative example 5

An aqueous dispersion (11), a masterbatch (15) and filaments (15) were obtained in the same manner as in example 1, except that only sorbitan fatty acid esters (RHEODOL SP-L10, manufactured by Kabushiki Kaisha, HLB value 8.6) were used as the amphipathic molecules.

Comparative example 6

(production of masterbatch and filament)

9 parts by mass of titanium oxide particles, 0.3 part by mass of polyglycerin fatty acid ester, 0.3 part by mass of polyoxyethylene alkyl ether and 0.3 part by mass of ethanol were directly mixed with 90.1 parts by mass of polypropylene without using an aqueous dispersion, and melt-kneaded in a twin-screw extruder to prepare a master batch (16), and the same procedure as in example 1 was followed to obtain filaments (16).

Comparative example 7

(production of filaments)

Instead of using both the aqueous dispersion and the master batch, 0.9 parts by mass of titanium oxide particles, 0.03 parts by mass of polyglycerin fatty acid ester, 0.03 parts by mass of polyoxyethylene alkyl ether and 0.03 parts by mass of ethanol were directly mixed with 99.01 parts by mass of polypropylene, and melt-kneaded in a spinning machine, followed by the same procedure as in example 1 to obtain filaments (17).

Comparative example 8

(production of film)

10 parts by mass of a master batch (16) was mixed with 90 parts by mass of polypropylene (Prime Polymer Co., ltd., "Y-2000 GV"), and then melt-molded at a film-forming temperature of 230℃by using a 20mm single screw extruder connected with a 100mm wide T die, to obtain a film (2) having a thickness of 10. Mu.m.

Next, the respective masterbatches, filaments and films obtained in examples 1 to 8 and comparative examples 1 to 8 were measured and evaluated by the following methods.

1. Evaluation of aggregated particles in masterbatch (anti-aggregation Property)

For the obtained master batches (1) to (16), a sintered filter having a filter diameter of 25 μm was provided at the screw tip end portion of a 25mm single screw extruder, and the pressure difference at the time of passing 1kg of the master batch was measured, and the case where the pressure difference was 1MPa or less was regarded as very good "", the case where 1 to 5MPa or less was regarded as good "", the case where the pressure difference was more than 5MPa and 10MPa or less was regarded as slightly bad "Δ", and the case where the pressure difference was not passed was regarded as bad "×".

2. Evaluation of filament spinnability

The filament breaking frequency at the time of spinning was evaluated for the filaments (1) to (17) obtained. This operation was performed 5 times on the same sample as an average value. The occurrence of the broken wire was defined as good ". Smallcircle.,. Sup.3 times or more and less than 10 times as slightly bad". Sup.Δ ", and 10 times or more as bad". Sup.x ".

3. Evaluation of aggregated particles in filaments (anti-aggregation Property)

The filaments (1) to (17) thus obtained were cut into 0.1g, pressed into a film shape by a glass slide (preparation), and then observed by an optical microscope (magnification: 200 times), to obtain particle images, and the particle diameters (circular equivalent diameters) were measured for at least 1000 particles (which may be primary particles or may further include secondary particles) randomly selected. When particles having a particle diameter of 20 μm or more were less than 1, the particles were regarded as excellent, 1 to 5 were regarded as excellent, 6 to 19 were regarded as slightly defective "Δ", and 20 or more were regarded as defective "X".

4. Evaluation of film Forming Property

The obtained films (1) to (2) were evaluated for stability at the time of film formation. A sintered filter having a filtration diameter of 20 μm was provided, and a film was formed from 10kg of the raw material, and the processability was evaluated. The case where film formation was completed without boosting was referred to as good, the case where film formation was completed with boosting was referred to as slightly bad "Δ", and the case where film formation was not performed even with boosting was referred to as bad "x".

5. Evaluation of aggregated particles in film (anti-aggregation Property)

The obtained films (1) to (2) were cut into 0.1g, pressed into a film shape by a slide glass, observed by an optical microscope (magnification: 200 times), and a particle image was obtained, and the particle diameters (equivalent circle diameters) of at least 1000 particles (primary particles or secondary particles) selected at random were measured. When particles having a particle diameter of 20 μm or more were less than 1, the particles were regarded as excellent, 1 to 5 were regarded as excellent, 6 to 19 were regarded as slightly defective "Δ", and 20 or more were regarded as defective "X".

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

[ Table 1A ]

[ Table 1B ]

[ Table 1C ]

[ Table 2A ]

[ Table 2B ]

From the results shown in tables 1A to 1C, it is understood that in examples 1 to 10, when the masterbatches (1) to (10) were produced using the aqueous dispersions (1) to (6) containing any of the polyglycerin fatty acid ester and the fatty acid alkanolamide and any of the polyglycerin fatty acid ester and the polyoxyethylene alkyl ether as the amphiphilic molecules, the pressure difference of the masterbatches was 5MPa or less, secondary aggregation of the metal oxide was prevented at the time of molding the masterbatches, and the dispersion stability of the metal oxide was high. In particular, it is found that in examples 1 to 4, 7 to 9 and 11, when polypropylene, high-density polyethylene, polyethylene terephthalate or polyamide-6 is used as the thermoplastic resins (A) and (B), the pressure difference of the master batch is 1MPa or less, secondary aggregation of the metal oxide can be sufficiently prevented in the master batch, and the dispersion stability of the metal oxide is extremely high.

In examples 1 to 10, the master batches (1) to (10) were produced using any of the aqueous dispersions (1) to (6), and when the filaments (1) to (10) were produced using the master batches, the occurrence of filament breakage was less than 3 times, and the spinning properties of the filaments were good.

Further, it was found that in examples 1 to 10, the use of any of the aqueous dispersions (1) to (6) produced masterbatches (1) to (10), and the use of the masterbatches produced filaments (1) to (10) produced with the masterbatches resulted in filaments having particles of 20 μm or more in size of 5 or less, secondary aggregation of metal oxides was prevented during filament molding, and the dispersion stability of metal oxides was high. In particular, in examples 1 to 4 and 7 to 10, when titanium oxide particles were used as the metal oxide, the number of particles having a particle diameter of 20 μm or more in the filaments was less than 1, and 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 master batch (1) was produced using the aqueous dispersion (1), and the film (1) was produced using the master batch, the film formation was completed without pressure boosting, and the film forming property of the film was good.

In example 11, it was found that when the master batch (1) was produced using the aqueous dispersion (1), and when the film (1) was produced using the master batch, the number of particles having a particle diameter of 20 μm or more was 1 to 5, and the secondary aggregation of the metal oxide was prevented during the film formation, and the dispersion stability of the metal oxide was high.

On the other hand, from the results of tables 2A to 2B, in comparative example 1, when the master batch (8) was produced using the aqueous dispersion (7) containing only the fatty acid alkanolamide as the amphiphilic molecule, the pressure difference of the master batch was in the range of more than 5MPa and 10MPa or less, and the aggregated particles were present in the master batch in a large amount, and the aggregation preventing property of the metal oxide was poor, compared with examples 1 to 10.

In comparative example 1, when the masterbatch (11) was produced using the aqueous dispersion (7) and the filaments (11) were produced using the masterbatch, the occurrence of yarn breakage was 3 or more times and less than 10 times, and the spinnability of the filaments was slightly poor.

Further, in comparative example 1, when the masterbatch (11) was produced using the aqueous dispersion (7), and the filaments (11) were produced using the masterbatch, the number of particles having a particle diameter of 20 μm or more in the filaments was 20 or more, and the aggregated particles were present in a large amount in the filaments, and the aggregation resistance of the metal oxide was poor, as compared with examples 1 to 10.

In comparative example 2, when the masterbatch (12) was produced using the aqueous dispersion (8) containing only the polyglycerin fatty acid ester as the amphiphilic molecule, the pressure difference of the masterbatch was in the range of more than 5MPa and 10MPa or less, and the aggregated particles were present in the masterbatch in a large amount and the aggregation preventing property of the metal oxide was poor as compared with examples 1 to 10.

In comparative example 2, when the masterbatch (12) was produced using the aqueous dispersion (8) and the filaments (12) were produced using the masterbatch, the occurrence of filament breakage was 3 or more times and less than 10 times, and the filament spinnability was slightly poor.

Further, in comparative example 2, when the masterbatch (12) was produced using the aqueous dispersion (8), and the filaments (12) were produced using the masterbatch, the number of particles having a particle diameter of 20 μm or more in the filaments was 20 or more, and the aggregated particles were present in a large amount in the filaments, and the aggregation resistance of the metal oxide was poor, as compared with examples 1 to 10.

In comparative example 3, when the masterbatch (13) was produced using the aqueous dispersion (9) containing both the fatty acid alkanolamide and the sorbitan fatty acid ester as the amphiphilic molecules, the pressure difference of the masterbatch was in the range of more than 5MPa and 10MPa or less, and the aggregated particles were present in the masterbatch in a large amount, and the aggregation resistance of the metal oxide was poor, as compared with examples 1 to 10.

In comparative example 3, when the masterbatch (13) was produced using the aqueous dispersion (9) and the filaments (13) were produced using the masterbatch, the occurrence of filament breakage was 3 or more times and less than 10 times, and the spinning properties of the filaments were slightly poor.

Further, in comparative example 3, when the masterbatch (13) was produced using the aqueous dispersion (9), and the filaments (13) were produced using the masterbatch, the number of particles having a particle diameter of 20 μm or more in the filaments was 20 or more, and the aggregated particles were present in a large amount in the filaments, and the aggregation resistance of the metal oxide was poor, as compared with examples 1 to 10.

In comparative example 4, when the masterbatch (14) was produced using the aqueous dispersion (10) containing both sorbitan fatty acid ester and polyglycerin fatty acid ester as amphiphilic molecules, the pressure difference of the masterbatch was in the range of more than 5MPa and 10MPa or less, and the aggregated particles were present in the masterbatch in a large amount, and the aggregation resistance of the metal oxide was poor, as compared with examples 1 to 10.

In comparative example 4, when the masterbatch (14) was produced using the aqueous dispersion (10) and the filaments (14) were produced using the masterbatch, the occurrence of yarn breakage was 3 or more times and less than 10 times, and the spinnability of the filaments was slightly poor.

Further, in comparative example 4, when the masterbatch (14) was produced using the aqueous dispersion (10) and the filament (14) was produced using the masterbatch, 20 or more particles having a particle diameter of 20 μm or more were contained in the filament, and the aggregated particles were present in a large amount in the filament and the aggregation resistance of the metal oxide was poor as compared with examples 1 to 10.

In comparative example 5, when the masterbatch (15) was produced using the aqueous dispersion (11) containing only the sorbitan fatty acid ester as the amphiphilic molecule, the pressure difference of the masterbatch was in the range of more than 5MPa and 10MPa or less, and the aggregated particles were present in the masterbatch in a large amount and the aggregation preventing property of the metal oxide was poor as compared with examples 1 to 10.

In comparative example 5, when the masterbatch (15) was produced using the aqueous dispersion (11), and the filaments (15) were produced using the masterbatch, the occurrence of filament breakage was 3 or more times and less than 10 times, and the filament spinnability was slightly poor.

Further, in comparative example 5, when the masterbatch (15) was produced using the aqueous dispersion (11), and the filaments (15) were produced using the masterbatch, the number of particles having a particle diameter of 20 μm or more in the filaments was 20 or more, and the aggregated particles were present in a large amount in the filaments, and the aggregation resistance of the metal oxide was poor, as compared with examples 1 to 10.

In comparative example 6, when a master batch (16) containing both polyglycerin fatty acid ester and polyoxyethylene alkyl ether as amphiphilic molecules was produced without using an aqueous dispersion, the master batch did not pass through a sintered filter, and a large amount of aggregated particles were present in the master batch, and the aggregation resistance of the metal oxide was poor.

In comparative example 6, the masterbatch (16) was produced without using an aqueous dispersion, and when the filament (16) was produced using the masterbatch, the occurrence of filament breakage was 10 times or more, and the spinning property of the filament was poor.

Further, in comparative example 6, when the masterbatch (16) was produced without using an aqueous dispersion, and the filament (16) was produced using the masterbatch, the number of particles having a particle diameter of 20 μm or more in the filament was 20 or more, and the aggregated particles were present in the filament in a large amount as compared with examples 1 to 10, and the aggregation resistance of the metal oxide was poor.

In comparative example 7, when the filaments (17) were produced without using both the aqueous dispersion and the master batch, the occurrence of filament breakage was 10 times or more, and the spinning property of the filaments was poor. In comparative example 7, when the filaments (17) were produced without using both the aqueous dispersion and the master batch, the number of particles having a particle diameter of 20 μm or more in the filaments was 20 or more, and the aggregation particles were present in the filaments in a very large amount as compared with examples 1 to 10, and the aggregation resistance of the metal oxide was poor.

In comparative example 8, when the master batch (16) was produced without using an aqueous dispersion and the film (2) was produced using the master batch, the film could not be produced even if the pressure was increased, and the film forming property of the film was inferior to that of example 11.

In comparative example 8, the masterbatch (16) was produced without using an aqueous dispersion, and when the masterbatch was used to produce the film (2), the number of particles having a particle diameter of 20 μm or more in the film was 20 or more, and the aggregated particles were present in the film in a large amount as compared with example 11, and the aggregation resistance of the metal oxide was poor.

Claims

1. A masterbatch, comprising:

thermoplastic resin (A),

An inorganic compound containing a metal oxide as a main component,

An amphipathic molecule (A) having an HLB (hydrophilic-lipophilic balance) value in the range of 1 to 8, and

an amphipathic molecule (B) having an HLB value in the range of 10 to 18.

2. The masterbatch according to claim 1, wherein the content of the amphiphilic molecule (a) is 0.01 mass% or more and 40 mass% or less, and the content of the amphiphilic molecule (B) is 0.01 mass% or more and 40 mass% or less, with the total mass of the thermoplastic resin (a), the inorganic compound, the amphiphilic molecule (a), and the amphiphilic molecule (B) in the masterbatch being 100 mass%.

3. The master batch according to claim 1 or 2, wherein the amphiphilic molecule (a) contains 1 or 2 or more selected from glycerol fatty acid esters, polyglycerol fatty acid esters, polyoxyethylene glycerol fatty acid esters, propylene glycol fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, fatty acid alkanolamides, polyoxyethylene lanolin/lanolin alcohol/beeswax derivatives, polyoxyethylene castor oil/hydrogenated castor oil, polyoxyethylene alkyl ethers, polyoxyethylene fatty acid esters, polyoxyethylene alkylamines, polyoxyethylene cetyl ethers, polyoxyethylene stearyl stearates, polyoxyethylene lauryl stearates, POE hydrogenated castor oil fatty acid esters, polyoxyethylene trimethylolpropane fatty acid esters.

4. A masterbatch according to claim 3, wherein the amphiphilic molecule (a) comprises 1 or 2 selected from polyglycerol fatty acid esters and fatty acid alkanolamides.

5. The master batch according to any one of claims 1 to 4, wherein the amphiphilic molecule (B) comprises 1 or 2 or more selected from the group consisting of polyglycerin fatty acid esters, polyoxyethylene glycerin fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, polyoxyethylene lanolin/lanolin alcohol/beeswax derivatives, polyoxyethylene castor oil/hydrogenated castor oil, polyoxyethylene sterols/hydrogenated sterols, polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene fatty acid esters, polyoxyethylene alkylamines, polyoxyethylene alkylamides, polyoxyethylene glycerin monostearate, POE hydrogenated castor oil fatty acid esters, polyoxyethylene trimethylolpropane fatty acid esters, sucrose fatty acid esters.

6. The masterbatch according to claim 5, wherein the amphiphilic molecule (B) comprises 1 or 2 selected from polyoxyethylene sorbitol fatty acid esters and polyoxyethylene alkyl ethers.

7. The masterbatch according to claim 1, wherein the thermoplastic resin (a) contains 1 or 2 or more selected from polyethylene terephthalate, polyamide 6, polypropylene, low-density polyethylene and polycarbonate.

8. A thermoplastic resin composition comprising the master batch according to any one of claims 1 to 7 and a thermoplastic resin (B).

9. The thermoplastic resin composition according to claim 8, wherein the content of the masterbatch is 1 mass% or more and 90 mass% or less, when the total mass of the masterbatch and the thermoplastic resin (B) in the thermoplastic resin composition is 100 mass%.

10. The thermoplastic resin composition according to claim 8 or 9, wherein the thermoplastic resin (B) contains 1 or more selected from polyethylene terephthalate, polyamide 6, polypropylene, linear low density polyethylene and polycarbonate.

11. A thermoplastic resin molded article obtained by melt molding the thermoplastic resin composition according to any one of claims 8 to 10.

12. A thermoplastic resin molded article obtained by blending the master batch according to any one of claims 1 to 7 with a thermoplastic resin (B).

13. The thermoplastic resin molded body according to claim 12, wherein the content of the masterbatch is 1 mass% or more and 90 mass% or less, when the total mass of the masterbatch and the thermoplastic resin (B) in the thermoplastic resin molded body is 100 mass%.

14. The thermoplastic resin molded body according to claim 12 or 13, wherein the thermoplastic resin (B) contains 1 or more selected from polyethylene terephthalate, polyamide 6, polypropylene, linear low density polyethylene and polycarbonate.

15. The thermoplastic resin molded body according to any one of claims 11 to 14, wherein the thermoplastic resin molded body is any one selected from the group consisting of filaments, staple fibers, nonwoven fabrics, hollow filaments, and films.

16. A method for producing a master batch, comprising the steps of:

17. A method for producing a thermoplastic resin composition, comprising the steps of: a masterbatch obtained by the production method according to claim 16, which is melt-mixed with the thermoplastic resin (B).

18. The method for producing a thermoplastic resin composition according to claim 17, wherein the master batch and the thermoplastic resin (B) are melt-mixed so that the content of the master batch is 1 mass% or more and 90 mass% or less, based on 100 mass% of the total mass of the master batch and the thermoplastic resin (B).

19. A method for producing a thermoplastic resin molded body, comprising the steps of: a thermoplastic resin composition obtained by the production method according to claim 17 or 18, which is melt-molded.

20. A method for producing a thermoplastic resin molded body, comprising the steps of: a masterbatch obtained by the production method according to claim 16, which is melt-mixed with the thermoplastic resin (B).

21. The method for producing a thermoplastic resin molded article according to claim 20, wherein the master batch and the thermoplastic resin (B) are melt-mixed so that the content of the master batch is 1 mass% or more and 90 mass% or less, based on 100 mass% of the total mass of the master batch and the thermoplastic resin (B).

22. The method for producing a thermoplastic resin molded article according to any one of claims 19 to 21, wherein the thermoplastic resin (B) and the master batch are used to mold any one selected from the group consisting of filaments, staple fibers, nonwoven fabrics, hollow fibers, and films.