Resin composition, molded body, aggregate, and method for producing molded body

Abstract

Provided are: a resin composition containing a polyamide including a xylylenediamine unit and a C11-14 α, ω−linear aliphatic dicarboxylic acid unit, and at least one compound selected from the group consisting of silicone resins, fluorine-containing compounds, two-dimensional layered substances, and high molecular weight polyethylenes; a molded body formed from the resin composition; an aggregate of the molded body; and a method for producing a molded body using the resin composition.

Description

Resin composition, molded article, aggregate, and method for producing molded article

[0001] The present invention relates to a resin composition, a molded article, an aggregate, and a method for producing a molded article.

[0002] Since polyamide is excellent in various properties, it is applied in various fields. For example, Patent Document 1 discloses a sliding member characterized by containing 0.1 to 50 parts by mass of cellulose fibers having an average fiber diameter of 10 μm or less and unmodified cellulose fibers or cellulose fibers in which a part of the hydroxyl groups derived from cellulose are modified with hydrophilic substituents with respect to 100 parts by mass of polyamide.

[0003] Japanese Patent Application Laid-Open No. 2022-171674

[0004] Here, in a molded article using such polyamide, excellent wear resistance is required. For example, molded articles such as films and filaments using conventional polyamide have a problem of low wear resistance and limited applications. In addition, excellent moldability is also required in the production of the above molded article.

[0005] An object of the present invention is to provide a resin composition from which a molded article excellent in wear resistance can be obtained and which is excellent in moldability in the production of the molded article, a molded article formed from the resin composition, an aggregate of the molded articles, and a method for producing a molded article using the resin composition.

[0006] Specific examples of representative embodiments of the present invention are shown below. <1> A resin composition comprising a polyamide containing xylylenediamine units and α,ω-linear aliphatic dicarboxylic acid units having 11 to 14 carbon atoms, and at least one compound selected from the group consisting of silicone resin, fluorine-containing compounds, two-dimensional layered materials, and high molecular weight polyethylene. <2> The resin composition according to <1>, wherein the xylylenediamine is metaxylylenediamine, paraxylylenediamine, or a mixture thereof. <3> The resin composition according to <1> or <2>, wherein the α,ω-linear aliphatic dicarboxylic acid having 11 to 14 carbon atoms contains dodecanediic acid. <4> The resin composition according to any one of <1> to <3>, wherein the compound comprises a two-dimensional layered material. <5> The resin composition according to any one of <1> to <4>, wherein the two-dimensional layered material is molybdenum disulfide. <6> A molded article formed from the resin composition according to any one of <1> to <5>. <7> A molded article according to <6>, which is a film, filament, or plate. <8> An aggregate of molded articles according to <6> or <7>, which is an aggregate of a laminated film, a resin fabric, a resin knitted fabric, a resin nonwoven fabric, a brush, or a wire. <9> A method for manufacturing a molded article, comprising melting and molding a resin composition according to any one of <1> to <5>.

[0007] The present invention provides a resin composition that yields a molded article with excellent wear resistance and excellent moldability in the manufacture of the molded article, a molded article formed from the resin composition, an assembly of the molded articles, and a method for manufacturing a molded article using the resin composition.

[0008] Hereinafter, embodiments for carrying out the present invention (hereinafter simply referred to as "these embodiments") will be described in detail. These embodiments are illustrative examples for explaining the present invention, and the present invention is not limited to these embodiments. In this specification, "~" is used to include the numerical values ​​before and after it as the lower and upper limits, respectively. In this specification, all physical properties and characteristic values ​​are given at 23°C unless otherwise specified. In this specification, preferred combinations of embodiments are more preferred embodiments.

[0009] In this specification, unless otherwise specified, the number-average molecular weight shall be the value measured by the following method. The number-average molecular weight (Mn) shall be determined from the value converted to standard polymethyl methacrylate (PMMA) by gel permeation chromatography (GPC). Two columns packed with styrene polymer as the packing material shall be used, and hexafluoroisopropanol (HFIP) with a sodium trifluoroacetate concentration of 2 mmol / L shall be used as the solvent, with a resin concentration of 0.02% by mass, a column temperature of 40°C, a flow rate of 0.3 mL / min, and measurement shall be performed using a refractive index detector (RI). A calibration curve shall be obtained by dissolving six levels of PMMA in HFIP and measuring the values.

[0010] In this specification, unless otherwise specified, the melting point (Tm) shall be the value measured according to differential scanning calorimetry (DSC) in accordance with ISO 11357. Using a differential scanning calorimeter, the resin is placed in the measurement pan of the differential scanning calorimeter, heated to a temperature above the melting point at a heating rate of 10°C / min under a nitrogen atmosphere, and then rapidly cooled before measurement. The measurement conditions are as follows: heating at a heating rate of 10°C / min, held at 280°C for 5 minutes, and then cooled to 100°C at a cooling rate of -5°C / min to determine the melting point (Tm). The differential scanning calorimeter used is the "DSC-60" manufactured by Shimadzu Corporation. If the measurement methods etc. described in the standards shown in this specification differ from year to year, unless otherwise specified, the standards as of January 1, 2024 shall be used.

[0011] (Resin Composition) The resin composition of this embodiment contains a polyamide containing xylylenediamine units and α,ω-linear aliphatic dicarboxylic acid units having 11 to 14 carbon atoms, and at least one compound selected from the group consisting of silicone resin, fluorine-containing compound, two-dimensional layered material, and high molecular weight polyethylene. The inventors have found that by adopting this specific configuration, a molded article with excellent wear resistance can be obtained, and the moldability in the manufacture of the molded article is excellent. The reason for obtaining the above effects is unknown, but it is presumed to be as follows. A resin composition using a polyamide containing xylylenediamine units and α,ω-linear aliphatic dicarboxylic acid units having 11 to 14 carbon atoms has excellent moldability, but it is thought to have poor wear resistance because the friction on the surface of the molded article is high. Therefore, it is thought that by including at least one compound selected from the group consisting of silicone resin, fluorine-containing compound, two-dimensional layered material, and high molecular weight polyethylene in the resin composition, the surface smoothness of the molded article is increased, and the wear resistance is improved.

[0012] The details of the resin composition of this embodiment will be described below. Hereinafter, polyamides containing xylylenediamine units and α,ω-linear aliphatic dicarboxylic acid units having 11 to 14 carbon atoms will also be referred to as "specific polyamides." Hereinafter, at least one compound selected from the group consisting of silicone resins, fluorine-containing compounds, two-dimensional layered materials, and high molecular weight polyethylene will also be referred to as "specific compounds."

[0013] <Specific Polyamide> The resin composition of this embodiment contains a polyamide (specific polyamide) comprising xylylenediamine units and α,ω-linear aliphatic dicarboxylic acid units having 11 to 14 carbon atoms. In this specification, constituent units derived from xylylenediamine are referred to as xylylenediamine units, constituent units derived from diamine are referred to as diamine units, constituent units derived from dicarboxylic acid are referred to as dicarboxylic acid units, and so on.

[0014] The specific polyamide preferably contains constituent units derived from diamines (diamine units) and constituent units derived from dicarboxylic acids (dicarboxylic acid units).

[0015] The content of xylylenediamine units in the total diamine units of a particular polyamide is preferably 70 mol% or more, more preferably 75 mol% or more, even more preferably 80 mol% or more, even more preferably 90 mol% or more, even more preferably 95 mol% or more, and particularly preferably 99 mol% or more.

[0016] The xylylenediamine in the xylylenediamine unit is preferably metaxylylenediamine, paraxylylenediamine, or a mixture thereof. The mixture preferably contains 0 to 100 mol% metaxylylenediamine and 100 to 0 mol% paraxylylenediamine (provided that the total of metaxylylenediamine and paraxylylenediamine does not exceed 100 mol%), more preferably 10 to 100 mol% metaxylylenediamine and 90 to 0 mol% paraxylylenediamine, even more preferably 10 to 90 mol% metaxylylenediamine and 90 to 10 mol% paraxylylenediamine, even more preferably 40 to 90 mol% metaxylylenediamine and 60 to 10 mol% paraxylylenediamine, and even more preferably 60 to 90 mol% metaxylylenediamine and 40 to 10 mol% paraxylylenediamine.

[0017] In the specific polyamide, it is preferable that the total of para-xylylenediamine units and meta-xylylenediamine units constitutes preferably 80 mol% or more, more preferably 85 mol% or more, even more preferably 90 mol% or more, even more preferably 95 mol% or more, even more preferably 98 mol% or more, and even more preferably 99 mol% or more of the diamine units. The upper limit of the total of the para-xylylenediamine units and meta-xylylenediamine units is 100 mol%. By setting the proportion of meta-xylylenediamine to 10 mol% or more, the appearance of the test specimen surface tends to improve when injection molded under low mold temperature conditions. Furthermore, by setting the proportion of para-xylylenediamine to 10 mol% or more, crystallization can be promoted at even lower mold temperatures.

[0018] Diamines other than metaxylylenediamine and paraxylylenediamine that can be used as raw material diamine components for specific polyamides include aliphatic diamines such as tetramethylenediamine, pentamethylenediamine, 2-methylpentanediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, dodecamethylenediamine, 2,2,4-trimethyl-hexamethylenediamine, and 2,4,4-trimethylhexamethylenediamine, as well as 1,3-bis(aminomethyl) Examples of alicyclic diamines such as cyclohexane, 1,4-bis(aminomethyl)cyclohexane, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, bis(4-aminocyclohexyl)methane, 2,2-bis(4-aminocyclohexyl)propane, bis(aminomethyl)decalin, and bis(aminomethyl)tricyclodecane, as well as aromatic ring-containing diamines such as bis(4-aminophenyl) ether, paraphenylenediamine, and bis(aminomethyl)naphthalene, can be used individually or in combination of two or more.

[0019] Furthermore, the specific polyamide preferably contains α,ω-linear aliphatic dicarboxylic acid units having 11 to 14 carbon atoms as dicarboxylic acid units. Preferably, 75 mol% or more, more preferably 80 mol% or more, even more preferably 85 mol% or more, even more preferably 90 mol% or more, even more preferably 95 mol% or more, and especially most preferably 99 mol% or more of the dicarboxylic acid units of the specific polyamide are derived from α,ω-linear aliphatic dicarboxylic acids having 11 to 14 carbon atoms.

[0020] As a C11-C14 α,ω-linear aliphatic dicarboxylic acid suitable for use as a raw material dicarboxylic acid component of a specific polyamide, C11-C13 α,ω-linear aliphatic dicarboxylic acids are preferred, and C12-C13 α,ω-linear aliphatic dicarboxylic acids are preferred. Specifically, C11-C14 α,ω-linear aliphatic dicarboxylic acids include undecanediic acid, dodecanediic acid, tridecanediic acid, tetradecanediic acid, etc. Among these, dodecanediic acid is preferred because it brings the melting point of the specific polyamide into a range suitable for molding.

[0021] Examples of dicarboxylic acid components other than those mentioned above include phthalate compounds such as isophthalic acid, terephthalic acid, and orthophthalic acid, and isomers of naphthalenedicarboxylic acids such as 1,2-naphthalenedicarboxylic acid, 1,3-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 1,6-naphthalenedicarboxylic acid, 1,7-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, and 2,7-naphthalenedicarboxylic acid, which can be used individually or in mixtures of two or more.

[0022] It should be noted that while the specific polyamide is mainly composed of diamine units and dicarboxylic acid units, it does not mean that other constituent units are completely excluded, and it goes without saying that it may also contain constituent units derived from lactams such as ε-caprolactam and laurolactam, and aliphatic aminocarboxylic acids such as aminocaproic acid and aminoundecanoic acid. Here, "main components" refers to the fact that among the constituent units constituting the specific polyamide, the total number of diamine units and dicarboxylic acid-derived constituent units is the largest among all constituent units. In this embodiment, it is preferable that the total of diamine units and dicarboxylic acid units in the specific polyamide accounts for 90% by mass or more of the total constituent units, more preferably 95% by mass or more, even more preferably 97% by mass or more, and even more preferably 99% by mass or more.

[0023] For specific polyamides, it is also preferable to use polyamides manufactured using biomass raw materials (biomass polyamide resins). By using biomass polyamide resins, the environmental impact can be reduced. It is also possible to use raw material monomers that have undergone mass balance certification (ISCC PLUS). Mass balance certification means that the extent to which renewable raw materials and bio-raw materials are used in each factory or production facility, and how much of the product is produced or shipped, is quantified and guaranteed along with quality.

[0024] The melting point of the specific polyamide is preferably 150°C or higher, more preferably 180°C or higher, even more preferably 200°C or higher, and preferably 350°C or lower, more preferably 330°C or lower, and even more preferably 300°C or lower.

[0025] The specific polyamide preferably has a lower limit of number-average molecular weight (Mn) of 6,000 or more, more preferably 8,000 or more, even more preferably 10,000 or more, and more preferably 100,000 or less, and more preferably 50,000 or less. Within this range, heat resistance, elastic modulus, dimensional stability, and moldability are improved.

[0026] The relative viscosity of the specified polyamide is preferably 1.9 or higher at the lower limit, more preferably 2.0 or higher, and even more preferably 2.1 or higher. On the other hand, the upper limit of the relative viscosity of the specified polyamide is preferably 4.0 or lower, more preferably 3.9 or lower, and even more preferably 3.8 or lower. The relative viscosity of the specified polyamide is measured under the conditions of JIS K 69020-2.

[0027] The content of the specific polyamide in the resin composition is preferably 40% by mass or more, more preferably 50% by mass or more, and may be 60% by mass or more depending on the application. Setting it above the lower limit tends to further improve fluidity during melting. The content of the specific polyamide in the resin composition is preferably 99% by mass or less, more preferably 95% by mass or less, and may be 90% by mass or less or 80% by mass or less depending on the application. The resin composition may contain only one type of specific polyamide or two or more types. When two or more types are included, it is preferable that the total amount is within the above range.

[0028] <Other Polyamides> The resin composition of this embodiment may further contain other polyamides that do not fall under the category of specific polyamides. The type of other polyamide is not particularly defined and may be an aliphatic polyamide or a semi-aromatic polyamide. Examples of aliphatic polyamides include polyamide 4, polyamide 46, polyamide 6, polyamide 66, polyamide 666, polyamide 610, polyamide 11, polyamide 12, etc. Semi-aromatic polyamides are composed of diamine-derived structural units and dicarboxylic acid-derived structural units, and it is preferable that 20 to 80 mol% (preferably 30 to 80 mol%, more preferably 40 to 70 mol%) of the total structural units of the diamine-derived structural units and dicarboxylic acid-derived structural units contain aromatic rings. By using such semi-aromatic polyamides, the mechanical strength of the resulting resin molded product can be increased. Examples of semi-aromatic polyamides include terephthalic acid-based polyamides (polyamide 6T, polyamide 6I / 6T, polyamide 9T, polyamide 10T), etc. In addition to the above, polyamides described in paragraphs 0012 to 0031 of Japanese Patent Publication No. 2022-139048 can also be used, and this information is incorporated herein.

[0029] The content of other polyamides in the resin composition is preferably 20% by mass or less, more preferably 10% by mass or less, and may be 5% by mass or less depending on the application. Furthermore, it may be 1% by mass or less, or 0.1% by mass or less. The resin composition may contain only one type of specific polyamide, or it may contain two or more types. When it contains two or more types, it is preferable that the total amount is within the above range.

[0030] <Specific Compounds> The resin composition of this embodiment contains at least one compound (specific compound) selected from the group consisting of silicone resin, fluorine-containing compound, two-dimensional layered material, and high molecular weight polyethylene. Among these, from the viewpoint of abrasion resistance, it is preferable that the resin composition of this embodiment contains a two-dimensional layered material as the specific compound.

[0031] [Silicone Resin] Examples of silicone resins used in this embodiment include silicone oil and silicone rubber. Here, the silicone resin is preferably an organopolysiloxane. The organopolysiloxane may be linear, branched, or network-like, but a linear organopolysiloxane is preferred, and its average composition formula is R ｍ SiO （４－ｍ） A linear organopolysiloxane represented by the above average composition formula is more preferred. In the above average composition formula, m is a number between 1.98 and 2.02, and R represents an organic group.

[0032] Examples of such organopolysiloxanes include polydimethylsiloxane, polymethylphenylsiloxane, alcohol-modified polydimethylsiloxane, carboxy-modified polydimethylsiloxane, amino-modified polydimethylsiloxane, epoxy-modified polydimethylsiloxane, fluorine-modified polydimethylsiloxane, or organopolysiloxanes obtained by graft polymerization of acrylic or vinyl acetate.

[0033] The silicone resin may also be used in a form supported on other resins such as polyamide or polyolefin.

[0034] The content of silicone resin relative to the total mass of the resin composition is preferably 0.1% by mass or more, more preferably 1% by mass or more, even more preferably 3% by mass or more, particularly preferably 5% by mass or more, and also preferably 30% by mass or less, more preferably 25% by mass or less, and may be 20% by mass or less. When the content of the specific polyamide is 100 parts by mass, the content of silicone resin is preferably 0.1% by mass or more, more preferably 1% by mass or more, even more preferably 3 parts by mass or more, even more preferably 5 parts by mass or more, particularly preferably 10 parts by mass or more, and also preferably 30 parts by mass or less, more preferably 25 parts by mass or less, and may be 20 parts by mass or less. The resin composition of this embodiment may contain only one type of silicone resin or may contain two or more types. When two or more types are included, it is preferable that the total amount is within the above range.

[0035] [Two-dimensional layered material] Examples of two-dimensional layered materials include molybdenum disulfide, tungsten disulfide, graphene, silicene, germanene, stanene, boron nitride, carbon nitride, etc., with molybdenum disulfide being preferred. Furthermore, it is preferable that the resin composition of this embodiment substantially contains no inorganic substances other than the two-dimensional layered material and the abrasive particles described later. Specifically, it is preferable that the content of inorganic substances that do not fall under either the two-dimensional layered material or the abrasive particles described later in the resin composition of this embodiment be 1% by mass or less, more preferably 0.1% by mass or less, and even more preferably 0.01% by mass or less.

[0036] The content of the two-dimensional layered material relative to the total mass of the resin composition is preferably 1% by mass or more, more preferably 2% by mass or more, even more preferably 3% by mass or more, preferably 20% by mass or less, more preferably 15% by mass or less, and may be 10% by mass or less. When the content of the specific polyamide is 100 parts by mass, the content of the two-dimensional layered material is preferably 1 part by mass or more, more preferably 2 parts by mass or more, even more preferably 3 parts by mass or more, preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and may be 10 parts by mass or less. The resin composition of this embodiment may contain only one type of two-dimensional layered material, or it may contain two or more types. When two or more types are included, it is preferable that the total amount is within the above range.

[0037] [High Molecular Weight Polyethylene] From the viewpoint of affinity with polyamides, high molecular weight polyethylene is preferably acid-modified polyethylene. Examples of acid-modifying groups include carboxyl groups, acid anhydride groups, and sulfonic acid groups, which may form salts, with acid anhydride groups being preferred. Furthermore, high molecular weight polyethylene may also have other modifying groups besides acid-modifying groups, such as amino groups, silanol groups, alkoxy groups, hydroxyl groups, epoxy groups, isocyanate groups, mercapto groups, and oxazoline groups.

[0038] The molecular weight of the high molecular weight polyethylene is preferably 50,000 or more, more preferably 100,000 or more, and even more preferably 200,000 or more. Furthermore, the molecular weight of the high molecular weight polyethylene is preferably 2,000,000 or less, more preferably 1,000,000 or less, and even more preferably 600,000 or less.

[0039] The content of high molecular weight polyethylene relative to the total mass of the resin composition is preferably 1% by mass or more, more preferably 2% by mass or more, even more preferably 3% by mass or more, preferably 20% by mass or less, more preferably 15% by mass or less, and may be 10% by mass or less. When the content of the specific polyamide is 100 parts by mass, the content of high molecular weight polyethylene is preferably 1 part by mass or more, more preferably 2 parts by mass or more, even more preferably 3 parts by mass or more, preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and may be 10 parts by mass or less. The resin composition of this embodiment may contain only one type of high molecular weight polyethylene, or it may contain two or more types. When two or more types are included, it is preferable that the total amount is within the above range.

[0040] [Fluorine-containing compound] The fluorine-containing compound is preferably a fluorine-containing resin, and more preferably polytetrafluoroethylene. Polytetrafluoroethylene may be a homopolymer of tetrafluoroethylene monomers or a copolymer with other monomers. Examples of other monomers include fluorine-containing olefins such as hexafluoropropylene, chlorotrifluoroethylene, fluoroalkylethylene, and perfluoroalkyl vinyl ether, and fluorine-containing alkyl (meth)acrylates such as perfluoroalkyl (meth)acrylate. These monomers can be used individually or in combination of two or more.

[0041] The content of the fluorine-containing compound relative to the total mass of the resin composition is preferably 5% by mass or more, more preferably 10% by mass or more, even more preferably 15% by mass or more, preferably 40% by mass or less, more preferably 35% by mass or less, and may also be 30% by mass or less. When the content of the specific polyamide is 100 parts by mass, the content of the fluorine-containing compound is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, even more preferably 15 parts by mass or more, preferably 50 parts by mass or less, more preferably 40 parts by mass or less, and may also be 35 parts by mass or less. The resin composition of this embodiment may contain only one type of fluorine-containing compound or two or more types. When two or more types are included, it is preferable that the total amount is within the above range.

[0042] <Abrasive Particles> Depending on the application of the resin composition, the resin composition of this embodiment may also contain abrasive particles. Known abrasive particles such as silicon carbide and aluminum oxide can be used as abrasive particles. The particle size of the abrasive particles should be determined according to the intended use of the molded body and the abrasive performance, but it is preferable that the particle size is F30 or higher, more preferably F36 or higher, and even more preferably F40 or higher in the particle size category of JIS R 6001-1:2017. The particle size of the abrasive particles is preferably F180 or lower, more preferably F200 or lower, and even more preferably F150 or lower. Furthermore, it is preferable that the particle size of the abrasive particles in the standard particle size distribution for fine powder for precision polishing in JIS R 6001-2 is #240 or higher, more preferably #280 or higher, and even more preferably #320 or higher. The particle size of the abrasive particles is preferably #300 or less, more preferably #2500 or less, and even more preferably #2000 or less.

[0043] Preferably, the content of the abrasive particles is 5% by mass or more, more preferably 10% by mass or more, still more preferably 15% by mass or more, and preferably 50% by mass or less, more preferably 40% by mass or less, and may be 30% by mass or less, based on the total mass of the resin composition. When the content of the specific polyamide is 100 parts by mass, the content of the abrasive particles is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, still more preferably 15 parts by mass or more, and preferably 100 parts by mass or less, more preferably 60 parts by mass or less, and may be 40 parts by mass or less. When the content of the specific compound is 100 parts by mass, the content of the abrasive particles is preferably 100 parts by mass or more, more preferably 200 parts by mass or more, still more preferably 300 parts by mass or more, and preferably 5000 parts by mass or less, more preferably 4500 parts by mass or less, and may be 4000 parts by mass or less. The resin composition of the present embodiment may contain only one kind of abrasive particles or may contain two or more kinds of abrasive particles. When two or more kinds are contained, the total amount preferably falls within the above range.

[0044] <Other Components> The resin composition of this embodiment may further contain other components. Preferably, the total of the specific polyamide, the specific compound, and the abrasive particles contained as needed in the resin composition of this embodiment accounts for 90% by mass or more of the resin composition, more preferably 95% by mass or more, and even more preferably 99% by mass or more. Examples of other components include resin additives such as heat stabilizers, light stabilizers, antioxidants, UV inhibitors, alkalis, colorants, hydrolysis resistance improvers, matting agents, plasticizers, dispersants, antistatic agents, gelation inhibitors, and flame retardants. The total amount of resin additives is preferably 20.0% by mass or less, more preferably 10.0% by mass or less, even more preferably 5.0% by mass or less, and even more preferably 1.0% by mass or less, based on the total mass of the resin composition. Only one type of other additive may be used, or two or more types may be used in combination. Details of other additives can be found in paragraphs 0130 to 0155 of Japanese Patent No. 4894982, and these contents are incorporated herein. Furthermore, the resin composition of this embodiment may contain additives described in paragraphs 0047 to 0103 of International Publication No. 2021 / 241471, without departing from the spirit of the present invention, and these contents are incorporated herein.

[0045] <Method for Manufacturing the Resin Composition> In this embodiment, the method for manufacturing the resin composition is not particularly specified, and a wide range of known methods for manufacturing thermoplastic resin compositions can be used. Specifically, the resin composition can be manufactured by pre-mixing each component using various mixers such as tumblers and Henschel mixers, and then melt-kneading them using a Banbury mixer, rolls, brabender, single-screw extruder, twin-screw extruder, kneader, etc.

[0046] Furthermore, for example, a resin composition can be manufactured by supplying the components to an extruder using a feeder, either without pre-mixing them or by pre-mixing only some of the components, and then melt-kneading them. In addition, for example, a composition obtained by pre-mixing some of the components and supplying it to an extruder for melt-kneading can be used as a masterbatch, and pellets can be manufactured by mixing this masterbatch with the remaining components again and melt-kneading it.

[0047] <Formed Body> The formed body of the present embodiment is a formed body formed from the resin composition of the present embodiment. As the formed body, it is preferably a film, a filament or a plate. The shape of the formed body is not particularly limited and can be appropriately selected according to the use and purpose of the molded product. For example, plate-like, plate-shaped, rod-shaped, sheet-shaped, film-shaped, cylindrical, annular, circular, elliptical, gear-shaped, polygonal-shaped, irregular-shaped products, hollow products, frame-shaped, box-shaped, panel-shaped ones, etc. can be mentioned. The manufacturing method of these formed bodies will be described later.

[0048] <Aggregate> The aggregate of the present embodiment is an aggregate of the formed bodies of the present embodiment, and is an aggregate that is a laminated film, a resin fabric, a resin knitted fabric, a resin non-woven fabric, a brush or a wire.

[0049] The laminated film preferably includes, as at least one layer (preferably two or more layers) among the laminated layers, the film which is the formed body of the present embodiment. Such an aspect includes, for example, a biaxially stretched laminated film that includes, as at least one layer of the laminated layers, the film which is the formed body of the present embodiment. The thickness of the layer in the laminated film, the thickness of the film itself, etc. are not particularly limited and may be set according to the use and the like.

[0050] The resin fabric, resin knitted fabric, and resin non-woven fabric preferably include the filament which is the formed body of the present embodiment as the yarns or fibers forming them. The shape, density, weaving texture, knitting texture, entanglement shape, other additives, etc. of the resin fabric, resin knitted fabric, or resin non-woven fabric are not particularly limited, and known ones can be used without particular limitation.

[0051] The brush preferably contains the filament, which is the molded body of this embodiment, as the bristle material. The shape of the brush is not particularly limited and examples include roll brushes, cup brushes, foil brushes, cylindrical brushes, etc. Furthermore, it can be any known shape without particular restriction, such as making the side surface of the filament wavy. Here, the brush preferably contains, for example, 100 parts by mass of a specific polyamide, 3 to 30 parts by mass of silicone resin, 1 to 20 parts by mass of a two-dimensional layered material, 1 to 20 parts by mass of high molecular weight polyethylene, and at least one compound selected from the group consisting of 5 to 50 parts by mass of a fluorine-containing compound, and 5 to 100 parts by mass of abrasive particles. The preferred range of content of these components is as described above.

[0052] Examples of wires include papermaking wires, and the filament, which is the molded body of this embodiment, can be obtained by known methods, such as by forming a plain weave or multi-layer weave in a known way.

[0053] The resin composition of this embodiment exhibits excellent moldability during the manufacturing of molded articles, thus enabling the easy production of various molded articles and improving the design flexibility of the molded articles. Furthermore, since the molded articles obtained from the resin composition of this embodiment exhibit excellent wear resistance, these molded articles are expected to have superior durability and other properties.

[0054] <Method for manufacturing molded articles and assemblies> The method for manufacturing the molded articles of this embodiment preferably includes melting and molding the resin composition of this embodiment. For example, the molded articles of this embodiment may be molded directly by various molding methods after melting and kneading each component, or the components may be melted and kneaded to form pellets, then melted again and molded by various molding methods.

[0055] The method for manufacturing the molded article of this embodiment is not particularly defined. As an example, an injection-molded product formed by injection molding is provided.

[0056] If the molded article of this embodiment is a film, it can be manufactured by known methods. For example, a masterbatch pellet containing a specific polyamide and a specific compound can be blended, and this blended pellet, along with abrasive particles as needed, can be supplied to an extruder to obtain a film by extrusion molding. The film may also be stretched by known methods after extrusion molding. Furthermore, the above-mentioned laminated film may be obtained by co-extrusion during extrusion molding, or by lamination molding.

[0057] When the molded body of this embodiment is a filament, it can be manufactured by known methods. For example, a masterbatch pellet containing a specific polyamide and a specific compound can be blended, and this blended pellet, along with abrasive particles as needed, can be supplied to a melt spinning machine to obtain a filament. Specifically, a monofilament can be obtained by extruding the melt-kneaded resin composition from the spinneret of a melt spinning machine and performing necessary treatments such as cooling and solidification, heat stretching, and heat alicyclic treatment. Alternatively, monofilaments can be bundled together to form a multifilament. Examples of such filament manufacturing methods include the method described in Figure 1 of Table 2017 / 010389. By weaving the filament obtained by the above methods, a resin woven fabric or wire such as a papermaking wire can be obtained; by knitting it, a resin knitted fabric can be obtained; and by nonwoven it, a resin nonwoven fabric can be obtained. Known methods can be used without particular limitation as these manufacturing methods. Furthermore, a brush can be obtained by implanting the filament obtained in this way onto, for example, at least one part of a brush base material. Known methods can be used without particular limitation as a manufacturing method for a brush using the filament.

[0058] If the molded body of this embodiment is a plate, it can be manufactured by known methods. For example, a masterbatch pellet containing a specific polyamide and a specific compound can be blended, and this blended pellet, along with abrasive particles as needed, can be supplied to an extruder, mold, etc., to obtain a plate.

[0059] The present invention will be described in more detail below with reference to examples. The materials, amounts used, proportions, processing content, processing procedures, etc., shown in the following examples can be modified as appropriate, as long as they do not depart from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. If the measuring instruments, etc., used in the examples are difficult to obtain due to discontinuation or other reasons, measurements can be taken using other instruments with equivalent performance.

[0060] (Example) <Synthesis of MP12> Dodecanedioic acid was placed in a jacketed reaction vessel equipped with a stirrer, condenser, condenser, thermometer, dropping tank, and nitrogen gas inlet tube, and after thorough nitrogen purging, it was heated to 180°C and melted. While stirring the contents, a mixed amine of metaxylylenediamine and paraxylylenediamine (molar ratio: 70:30) (manufactured by Mitsubishi Gas Chemical Co., Ltd., MPXDA) was gradually added dropwise so that the molar ratio with adipic acid was 1:1, and the temperature was raised to 250°C. After the dropwise addition was completed, the process was continued for 20 minutes. Thereafter, the pressure inside the reaction system was continuously reduced to 0.08 MPa and the reaction was continued. After the reaction was completed, the reaction vessel was pressurized to 0.2 MPa with nitrogen gas, and the polymer was removed as strands from a nozzle at the bottom of the polymerization tank, and after water cooling, it was pelletized in a pelletizer to obtain the polymer. The melting point of the obtained MP12 was 207°C.

[0061] <Synthesis of MP10> Sebacic acid (manufactured by CASDA) was added to a jacketed reaction vessel equipped with a stirrer, condenser, condenser, thermometer, dropping tank, and nitrogen gas inlet tube. After thorough nitrogen purging, it was heated to 170°C and melted. While stirring the contents, a mixed amine of metaxylylenediamine and paraxylylenediamine (molar ratio: 70:30) (manufactured by Mitsubishi Gas Chemical Co., Ltd., MPXDA) was gradually added dropwise to achieve a molar ratio of 1:1 with sebacic acid, while the temperature was raised to 240°C. After the dropwise addition was complete, the temperature was raised to 260°C and continued for 20 minutes. Subsequently, the internal pressure of the reaction system was continuously reduced to 0.08 MPa, and the reaction was continued. After the reaction was complete, the reaction vessel was pressurized with nitrogen gas to 0.2 MPa, and the polymer was removed as strands from a nozzle at the bottom of the polymerization tank. After water cooling, it was pelletized in a pelletizer to obtain the polymer. The melting point of the obtained MP10 was 215°C.

[0062] <Manufacturing of Resin Composition> In each example or comparative example, each component listed in the table below was weighed out in the proportions indicated in the "parts by mass" column of the table (the proportion of each component is in mass%), blended in a tumbler, and fed into a twin-screw extruder (manufactured by Japan Steel Works, Ltd., TEX34αIII) from the base, melted, and resin composition pellets were produced. The temperature setting of the twin-screw extruder was 200 to 220°C.

[0063] <Evaluation of Wear Resistance> After drying the pellets obtained by the above manufacturing method at 120°C for 4 hours, a 100 x 100 x 2 mm flat plate was injection molded using a Sumitomo Heavy Industries SE130DU-HP. At this time, the cylinder temperature was 220°C and the mold temperature was 40°C. Furthermore, the flat plate was machined to a size of 30 x 30 mm. Referring to JIS K 7218:1986(A) method, a ring-on-disk friction wear test was performed in an environment of 23°C and 50% humidity with a ring speed of 0.5 m / s, measurement time of 6000 seconds, sliding distance of 3 km, applied pressure of 300 N, and surface pressure of 1.5 N / mm. ２ The test was conducted under the specified conditions, and the amount of wear was measured as the weight reduction from the original weight of the machined test piece after the test. The obtained wear amount was evaluated according to the following evaluation criteria. The evaluation results are recorded in the "Wear Resistance" column of the table. -Evaluation Criteria- A: Wear amount was 1g or less. B: Wear amount was greater than 1g and 5g or less. C: Wear amount exceeded 5g.

[0064] <Evaluation of moldability> The pellets obtained by the above manufacturing method were dried at 120°C for 4 hours, then supplied to an extruder-type melt spinning machine, melted and kneaded at a temperature of the melting point of polyamide + 20°C, and then extruded from the die hole. Next, the extruded filament was cooled and solidified in a cooling bath at 90°C, and then subsequently stretched to 3.0 times its original size in a hot air atmosphere at 150°C to obtain a circular cross-section filament with a diameter of 1.0 mm. Evaluation was performed according to the evaluation criteria below, and the evaluation results are recorded in the "Moldability" column of the table. -Evaluation Criteria- A: No filament breakage occurs. B: Filament breakage occurs occasionally. C: Filament breakage occurs frequently.

[0065]

[0066] Details of each component listed in the table are as follows:

[0067] [Polyamide] ・MP12: The above synthetic product ・MP10: The above synthetic product

[0068] [Silicone Resins] ・Multibase MB50-011 (manufactured by DuPont): 50% silicone, 50% polyamide 6 (as a carrier) ・Rikemaster SB-002E (manufactured by Riken Vitamin Co., Ltd.): 50% silicone, 50% polyethylene (as a carrier)

[0069] [Two-dimensional layered material] ・Molybdenum disulfide

[0070] [High molecular weight polyethylene] ・Lubmer LY1040 (manufactured by Mitsui Chemicals, Inc.)

[0071] [Fluorine-containing compounds] ・PTFE: Polytetrafluoroethylene (Model number: Dynion PTFE Micropowder TF9205, manufactured by 3M)

[0072] From the above results, it can be seen that the resin composition of this embodiment yields a molded article with excellent abrasion resistance and excellent moldability in the manufacture of the molded article. In Comparative Example 1, which does not contain the specific compound, it can be seen that the abrasion resistance is inferior. In Comparative Example 2, which does not contain the specific polyamide, it can be seen that the moldability is inferior.

Claims

1. A resin composition comprising a polyamide containing xylylenediamine units and α,ω-linear aliphatic dicarboxylic acid units having 11 to 14 carbon atoms, and at least one compound selected from the group consisting of silicone resins, fluorine-containing compounds, two-dimensional layered materials, and high molecular weight polyethylene.

2. The resin composition according to claim 1, wherein the xylylenediamine is metaxylylenediamine, paraxylylenediamine, or a mixture thereof.

3. The resin composition according to claim 1 or 2, wherein the α,ω-linear aliphatic dicarboxylic acid having 11 to 14 carbon atoms comprises dodecanediic acid.

4. The resin composition according to any one of claims 1 to 3, wherein the compound comprises a two-dimensional layered material.

5. The resin composition according to any one of claims 1 to 4, wherein the two-dimensional layered material is molybdenum disulfide.

6. A molded article formed from the resin composition according to any one of claims 1 to 5.

7. The molded article according to claim 6, which is a film, filament, or plate.

8. An aggregate of molded articles according to claim 6 or 7, wherein the aggregate is a laminated film, a resin fabric, a resin knitted fabric, a resin nonwoven fabric, a brush, or a wire.

9. A method for producing a molded article, comprising melting and molding a resin composition according to any one of claims 1 to 5.

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