Thermoplastic resin composition, molded body, production method for thermoplastic resin composition, and evaluation method for thermoplastic resin composition

Abstract

The purpose of the present disclosure is to provide a thermoplastic resin composition having good processability, a molded body, and a production method for the thermoplastic resin composition. The present disclosure is a thermoplastic resin composition which contains a resin (A) and a thermoplastic resin (B), wherein the resin (A) contains a structural unit represented by formula 1, and the dispersed particle diameter of the resin (A) is 1-100 μm. Formula 1: -X-(CR1R2)n-Y-(CR3R4)m-Z-

Description

Thermoplastic resin composition, molded article, method for producing thermoplastic resin composition, and method for evaluating thermoplastic resin composition

[0001] The present disclosure relates to a thermoplastic resin composition, a molded article, a method for producing a thermoplastic resin composition, and a method for evaluating a thermoplastic resin composition.

[0002] In the processing of melt-processable thermoplastic resins, high-speed extrusion is necessary to improve productivity and reduce costs. However, melt-processable thermoplastic resin compositions always have a critical shear rate, and if this rate is exceeded, a condition called melt fracture occurs, resulting in a rough surface, making it impossible to obtain good molded products.

[0003] As a method for improving the processability of thermoplastic resins, for example, Patent Document 1 proposes a method using ethylene vinyl alcohol, and Patent Document 2 proposes a method using a surfactant and polyethylene glycol, but the effects are not sufficient.

[0004] Japanese Patent Application Publication No. 2023 / 0031000

[0005] The present disclosure aims to provide a thermoplastic resin composition having good processability, a molded article, and a method for producing the thermoplastic resin composition. Another object of the present disclosure is to provide a method for evaluating a thermoplastic resin composition that can evaluate the dispersed particle size of the resin with high accuracy.

[0006] The present disclosure (1) is a thermoplastic resin composition comprising a resin (A) and a thermoplastic resin (B), wherein the resin (A) comprises a structural unit represented by the following formula 1, and the dispersed particle diameter of the resin (A) is 1 to 100 μm: １ R ２ ) ｎ -Y-(CR ３ R ４ ) ｍ-Z- (Formula 1) (In Formula 1, X represents a single bond or a divalent group which may have a functional group, Y and Z each independently represent a single bond, —O—, —C(═O)—, —C(═O)O—, —OC(═O)O—, —C(═NR′)—, —C(═NR′)O—, —OC(═NR′)O—, —S—, —S(═O)—, —S(═O)O—, —OS(═O)O—, or —S(═O) ２ -, -S(=O) ２ O-, -OS (=O) ２ O-, -P(=O)-, -P(=O)O-, -OP(=O)O-, -P(=O) ２ -, -P(=O) ２ O-, -OP (=O) ２ a group consisting of at least one selected from the group consisting of O—, —NR′—, and —C(OR′)R′— (wherein R′ is independently in each occurrence a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms); R １ , R ２ , R ３ and R ４ are each independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms; n and m are each independently an integer of 0 to 10; and at least one of X, Y, and Z is —C(═O)—, —C(═O)O—, —OC(═O)O—, or —C(OR′)R′—.

[0007] The present disclosure (2) is the thermoplastic resin composition according to the present disclosure (1), which is substantially free of fluorine.

[0008] The present disclosure (3) is a compound in which, in the formula 1, X is X １ and X ２ is a divalent group consisting of at least one selected from the group consisting of １ is -C(=O)-, -C(=NR')-, -S(=O) ２ a group consisting of at least one selected from the group consisting of -, -NR'-, -CR'R'-, and -C(OR')R'- (wherein R' is independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms in each occurrence); X ２ is an aromatic hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, in the thermoplastic resin composition according to the present disclosure (1) or (2).

[0009] The present disclosure (4) is the thermoplastic resin composition according to the present disclosure (3), wherein in formula 1, X is a divalent group containing at least one selected from the group consisting of -C(=O)-, -CR'R'-, and -C(OR')R'- (wherein R' is independently in each occurrence a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms).

[0010] The present disclosure (5) is the thermoplastic resin composition according to any one of the present disclosures (1) to (4), wherein in formula 1, Y and Z are each independently a single bond, —O—, —C(═O)—, —C(═O)O—, —C(═NR′)—, —C(═NR′)O—, —S—, —S(═O)2-, —S(═O)2O—, —NR′—, and —C(OR′)R′- (wherein R′ is independently, in each occurrence, a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms).

[0011] The present disclosure (6) is the thermoplastic resin composition according to the present disclosure (5), wherein, in the formula 1, Y and Z are each independently a group consisting of at least one selected from the group consisting of a single bond, —O—, —C(═O)—, and —C(═O)O—.

[0012] The present disclosure (7) is the thermoplastic resin composition according to any one of the present disclosures (1) to (6), wherein the resin (A) is at least one selected from the group consisting of an ethylene-vinyl alcohol copolymer and a polylactic acid.

[0013] The present disclosure (8) is the thermoplastic resin composition according to any one of the present disclosures (1) to (7), wherein the dispersed particle diameter of the resin (A) is 5 to 100 μm.

[0014] The present disclosure (9) is the thermoplastic resin composition according to any one of the present disclosures (1) to (8), wherein the thermoplastic resin (B) is a polyolefin resin.

[0015] The present disclosure (10) is the thermoplastic resin composition according to any one of the present disclosures (1) to (9), wherein the thermoplastic resin (B) is a metallocene-catalyzed linear low-density polyethylene.

[0016] The present disclosure (11) is the thermoplastic resin composition according to any one of the present disclosures (1) to (10), wherein the thermoplastic resin composition is a masterbatch and the content of the resin (A) is 8 to 50 mass%.

[0017] The present disclosure (12) is the thermoplastic resin composition according to any one of the present disclosures (1) to (10), wherein the thermoplastic resin composition comprises a masterbatch containing the resin (A) and the thermoplastic resin (B), and a thermoplastic resin (C), and the content of the resin (A) is 0.1 to 1.0 mass%.

[0018] The present disclosure (13) is the thermoplastic resin composition according to the present disclosure (12), wherein the thermoplastic resin (C) is a metallocene-catalyzed linear low-density polyethylene.

[0019] The present disclosure (14) is a molded article using the thermoplastic resin composition according to any one of the present disclosures (1) to (13).

[0020] The present disclosure (15) is the molded article according to the present disclosure (14) which is in the form of a tube, a film, or a sheet.

[0021] The present disclosure (16) is a method for producing the thermoplastic resin composition according to any one of the present disclosures (1) to (13), including a mixing step of mixing the resin (A) and the thermoplastic resin (B) using a twin-screw extruder.

[0022] The present disclosure (17) is the method for producing a thermoplastic resin composition according to the present disclosure (16), wherein the twin-screw extruder comprises a screw having a plurality of screw elements, including two or more kneading disc elements, attached to a shaft, and a barrel incorporating the two screws, and a kneading area ratio, which is the value obtained by dividing the total length of the kneading disc elements by the total length of the screws, is 0.01 or more.

[0023] The present disclosure (18) is a method for evaluating a thermoplastic resin composition, comprising: a melting step of heating a thermoplastic resin composition containing a resin (A) and a thermoplastic resin (B) to 180 to 200°C at a heating rate of 5 to 15°C / min, and then allowing the composition to stand for 3 to 10 minutes to melt the composition; and an observation step of observing the melted thermoplastic resin composition with a polarizing microscope to evaluate the dispersed particle size of the resin (A).

[0024] According to the present disclosure, it is possible to provide a thermoplastic resin composition having good processability, a molded article, and a method for producing the thermoplastic resin composition. Also, according to the present disclosure, it is possible to provide a method for evaluating a thermoplastic resin composition that can evaluate the dispersed particle size of a resin with high accuracy.

[0025] FIG. 1 is a schematic diagram showing the configuration of a twin-screw extruder used in melt-kneading in the examples.

[0026] The present disclosure will be specifically described below.

[0027] <Thermoplastic Resin Composition> The thermoplastic resin composition of the present disclosure includes a resin (A) and a thermoplastic resin (B), wherein the resin (A) includes a structural unit represented by the following formula 1, and the dispersed particle diameter of the resin (A) is 1 to 100 μm: １ R ２ ) ｎ -Y-(CR ３ R ４ ) ｍ -Z- (Formula 1) (In Formula 1, X represents a single bond or a divalent group which may have a functional group, Y and Z each independently represent a single bond, —O—, —C(═O)—, —C(═O)O—, —OC(═O)O—, —C(═NR′)—, —C(═NR′)O—, —OC(═NR′)O—, —S—, —S(═O)—, —S(═O)O—, —OS(═O)O—, or —S(═O) ２ -, -S(=O) ２ O-, -OS (=O) ２ O-, -P(=O)-, -P(=O)O-, -OP(=O)O-, -P(=O) ２ -, -P(=O) ２ O-, -OP (=O) ２a group consisting of at least one selected from the group consisting of O—, —NR′—, and —C(OR′)R′— (wherein R′ is independently in each occurrence a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms); R １ , R ２ , R ３ and R ４ are each independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms; n and m are each independently an integer of 0 to 10; and at least one of X, Y, and Z is —C(═O)—, —C(═O)O—, —OC(═O)O—, or —C(OR′)R′—.

[0028] The thermoplastic resin composition of the present disclosure provides good processability. In particular, it provides good extrusion processability even in long-run molding. The thermoplastic resin composition of the present disclosure was developed based on the discovery that the dispersed particle size of the resin (A) is strongly correlated with processability, and that particularly good processability is obtained when the dispersed particle size of the resin (A) is within a specific range.

[0029] In the above formula 1, X is X １ and X ２ is a divalent group consisting of at least one selected from the group consisting of １ is -C(=O)-, -C(=NR')-, -S(=O) ２ a group consisting of at least one selected from the group consisting of -, -NR'-, -CR'R'-, and -C(OR')R'- (wherein R' is independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms in each occurrence); X ２ is preferably an aromatic hydrocarbon group having 1 to 12 carbon atoms which may have a substituent.

[0030] In the above formula 1, X is more preferably a divalent group containing at least one selected from the group consisting of -C(=O)-, -CR'R'-, and -C(OR')R'- (wherein R' is independently in each occurrence a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms).

[0031] In the above formula 1, R' is, independently in each occurrence, preferably a hydrogen atom or a hydrocarbon group having 1 to 7 carbon atoms, more preferably a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, and even more preferably a hydrogen atom or a hydrocarbon group having 1 carbon atom.

[0032] In the above formula 1, Y and Z each independently represent a single bond, —O—, —C(═O)—, —C(═O)O—, —C(═NR′)—, —C(═NR′)O—, —S—, or —S(═O) ２ -, -S(=O) ２ It is preferably a group composed of at least one selected from the group consisting of O—, —NR′—, and —C(OR′)R′— (wherein R′ is independently in each occurrence a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms).

[0033] In the above formula 1, it is preferable that Y and Z each independently represent at least one group selected from the group consisting of a single bond, —O—, —C(═O)—, and —C(═O)O—.

[0034] In the above formula 1, R １ , R ２ , R ３ and R ４ are each independently preferably a hydrogen atom or a hydrocarbon group having 1 to 7 carbon atoms, more preferably a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, and even more preferably a hydrogen atom or a hydrocarbon group having 1 carbon atom.

[0035] n and m are each independently preferably an integer of 0 to 8, more preferably an integer of 0 to 6, even more preferably an integer of 0 to 4, and particularly preferably an integer of 0 to 2.

[0036] Resin (A) may contain a structural unit other than the structural unit represented by Formula 1. Examples of structural units that may be contained other than the structural unit represented by Formula 1 include glycol compounds such as ethylene glycol, propylene glycol, butanediol, heptanediol, hexanediol, octanediol, nonanediol, decanediol, 1,4-cyclohexanedimethanol, neopentyl glycol, glycerin, pentaerythritol, bisphenol A, polyethylene glycol, polypropylene glycol, and polytetramethylene glycol; oxalic acid, adipic acid, sebacic acid, azelaic acid, dodecanedioic acid, malonic acid, glutaric acid, cyclohexanedicarboxylic acid, terephthalic acid, methylparaben ... Examples of structural units include those derived from dicarboxylic acids such as benzoic acid, isophthalic acid, phthalic acid, naphthalenedicarboxylic acid, bis(p-carboxyphenyl)methane, anthracene dicarboxylic acid, 4,4'-diphenyl ether dicarboxylic acid, 5-sodium sulfoisophthalic acid, and 5-tetrabutylphosphonium isophthalic acid; hydroxycarboxylic acids such as glycolic acid, hydroxypropionic acid, hydroxybutyric acid, hydroxyvaleric acid, hydroxycaproic acid, and hydroxybenzoic acid; and lactones such as caprolactone, valerolactone, propiolactone, undecalactone, and 1,5-oxepan-2-one.

[0037] In the resin (A), the content of the structural unit represented by formula 1 is preferably 0.1% by mass or more, more preferably 1% by mass or more, even more preferably 10% by mass or more, and particularly preferably 20% by mass or more, and is preferably 99.9% by mass or less, more preferably 99% by mass or less, and even more preferably 95% by mass or less.

[0038] Examples of the resin (A) include polylactic acid (PLA), polybutylene succinate (PBS), ethylene-vinyl alcohol copolymer (EVOH), polybutylene succinate adipate (PBSA), etc. The resin (A) is preferably at least one selected from the group consisting of PLA, PBS, EVOH, and PBSA, more preferably at least one selected from the group consisting of PLA, PBS, and EVOH, and even more preferably at least one selected from the group consisting of PLA and EVOH.

[0039] The ethylene content of the ethylene-vinyl alcohol copolymer is preferably 10 mol% or more, more preferably 20 mol% or more, even more preferably 30 mol% or more, and is preferably 60 mol% or less, more preferably 50 mol% or less, even more preferably 40 mol% or less. Within the above ranges, the effect of improving processability is more excellent. In this specification, the ethylene content is determined by nuclear magnetic resonance (NMR) spectroscopy.

[0040] The ethylene-vinyl alcohol copolymer is preferably one obtained by saponifying an ethylene-vinyl ester copolymer, and among these, one obtained by saponifying an ethylene-vinyl acetate copolymer is particularly preferred.

[0041] The saponification degree of the ethylene-vinyl alcohol copolymer is preferably 80 to 100 mol %.

[0042] When copolymerizing ethylene and vinyl acetate, other fatty acid vinyl esters (such as vinyl propionate and vinyl pivalate) can also be used in combination. Furthermore, the ethylene-vinyl alcohol copolymer can contain 0.0002 to 0.2 mol % of a vinylsilane compound as a copolymerization component. Examples of vinylsilane compounds include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri(β-methoxyethoxy)silane, and γ-methacryloxypropylmethoxysilane. Of these, vinyltrimethoxysilane and vinyltriethoxysilane are preferred.

[0043] When copolymerizing ethylene and vinyl acetate, it is also possible to coexist in small amounts with monomers other than the above-mentioned fatty acid vinyl esters and vinylsilane compounds, such as α-olefins such as propylene, isobutylene, α-octene, and α-dodecene; unsaturated acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, and itaconic acid, or anhydrides, salts, or mono- or dialkyl esters thereof; nitriles such as acrylonitrile and methacrylonitrile; amides such as acrylamide and methacrylamide; olefin sulfonic acids such as ethylene sulfonic acid, allyl sulfonic acid, and methallylsulfonic acid, or salts thereof; alkyl vinyl ethers, vinyl ketone, N-vinylpyrrolidone, vinyl chloride, and vinylidene chloride.

[0044] The melting point of the resin (A) is preferably 65°C or higher, more preferably 70°C or higher, even more preferably 75°C or higher, still more preferably 80°C or higher, and preferably 190°C or lower, more preferably 185°C or lower, even more preferably 180°C or lower. Within the above range, the effect of improving processability is better. In this specification, the melting point is the temperature corresponding to the maximum value in the heat of fusion curve when the temperature is increased at a rate of 10°C / min using a differential scanning calorimetry (DSC) device.

[0045] The melt flow rate (MFR) of the resin (A) is preferably 0.001 g / 10 min or more, more preferably 0.01 g / 10 min or more, even more preferably 0.05 g / 10 min or more, even more preferably 0.1 g / 10 min or more, and particularly preferably 0.5 g / 10 min or more, and is preferably 500 g / 10 min or less, more preferably 300 g / 10 min or less, even more preferably 150 g / 10 min or less, even more preferably 40 g / 10 min or less, even more preferably 20 g / 10 min or less, and particularly preferably 10 g / 10 min or less. Within the above ranges, the effect of improving processability is more excellent. In this specification, MFR is measured in accordance with ASTM D 1238 under conditions of 190 ° C and a load of 2.16 kgf.

[0046] The weight average molecular weight of the resin (A) is preferably 80,000 or more, more preferably 100,000 or more, from the viewpoint of improving processability, and from the same viewpoint, is preferably 400,000 or less, more preferably 350,000 or less. The weight average molecular weight of the resin (A) can be determined by conversion using gel permeation chromatography (GPC) using chloroform as a solvent, a high-temperature SEC column (GMHHR-H series) manufactured by Tosoh Corporation as a column, a flow rate of 1.0 mL / min, a column temperature of 40°C, a differential refractive index detector (RI) as a detector, and polystyrene having a known molecular weight as a reference.

[0047] Examples of the thermoplastic resin (B) include polyolefin polymers (polyethylene (PE), polypropylene (PP), ethylene-propylene copolymers), polystyrene (PS), AS (acrylonitrile styrene) resins (AS), ABS (acrylonitrile butadiene styrene) resins (ABS), methacrylic resins (PMMA), polymethylpentene (PMP), butadiene resins (BDR), polybutene-1 (PB-1), polyvinyl alcohol (PVA), polyacrylonitrile (PAN), polymethacrylic styrene (MS), ethylene-vinyl acetate copolymers (EVA), ethylene-vinyl alcohol copolymers, and polyvinyl chloride (PVC). These may be used alone or in combination of two or more. Polyolefin polymers (polyolefin resins) are preferred because they provide a better effect of improving processability.

[0048] Among polyolefin polymers, for example, homopolymers (e.g., homopolymers of C2 to C10 α-olefins, preferably C2 to C6 α-olefins) can be mentioned. Specific examples of homopolymers include homopolyethylene and polypropylene (hPP). For example, homopolyethylene can be produced by free radical polymerization in a high-pressure process, and is typically a highly branched ethylene homopolymer, often known as LDPE (low density polyethylene), with a density of 0.945 g / cm. ３ less than, often 0.935 g / cm ３or less, for example, 0.900, 0.905, or 0.910 g / cm ３ to 0.920, 0.925, 0.927, 0.930, 0.935, or 0.945 g / cm ３ Unless otherwise noted herein, all polymer density values ​​are determined in accordance with ASTM D1505. Samples are molded under ASTM D4703-10a, Procedure C, and aged under ASTM D618-08 (23±2°C and 50±10% relative humidity) for 40 hours before testing.

[0049] In another example, ethylene monomer can be polymerized using known gas, slurry, and / or solution phase polymerizations, e.g., catalysts such as chromium-based catalysts, or single-site catalysts such as Ziegler-Natta and / or metallocene catalysts, all of which are well known in the polymerization art and will not be discussed further herein. When a more highly linear ethylene homopolymer is produced (e.g., using gas or slurry phase polymerization with any of the above catalysts), it is referred to as HDPE (high density polyethylene), and typically has a density of 0.945 to 0.970 g / cm. ３ 0.945 g / cm ３ It has a density of more than 10 ...

[0050] Further exemplary polymers include copolymers of two or more C2 to C40 α-olefins, such as C2 to C20 α-olefins, such as ethylene-α-olefin copolymers, or propylene-α-olefin copolymers (e.g., propylene-ethylene copolymers or propylene-ethylene-diene terpolymers (sometimes known as EPDM or PEDM)). Specific examples contemplated herein include copolymers of ethylene and one or more C3 to C20 α-olefin comonomers, such as C4 to C12 α-olefin comonomers, with 1-butene, 1-hexene, 1-octene, or mixtures of two or more thereof being preferred in various embodiments. The ethylene copolymer (e.g., copolymers of ethylene and one or more C3 to C20 α-olefins) can comprise ethylene-derived units in an amount of at least 90, 94, 95, or 96 wt % (e.g., ranging from a low of 80, 85, 90, 80, 85, 93, 93, 95, 96, or 97 wt % to a high of 94, 95, 95.5, 91, 92, 97, 94, 97.5, or 98 wt %), including a range from any lower value to any upper value, based on the total amount of ethylene-derived units and comonomer-derived units. For example, the ethylene copolymer can comprise ethylene-derived units in an amount of at least 90, 94, 95, 95, or 96 wt % (e.g., ranging from a low of 80, 85, 90, 80, 85, 93, 93, 95, 96, or 97 wt % to a high of 94, 95, 95.5, 91, 92, 97, 94, 97.5, or 98 wt %), including a range from any lower value to any upper value, based on the total amount of ethylene-derived units and comonomer-derived units. The copolymer may contain from 94 or 95% to 97 or 98% by weight of ethylene-derived units. The balance of the copolymer (based on ethylene-derived units and comonomer-derived units) consists of comonomer-derived units. For example, comonomer units (e.g., units derived from C2 to C20 α-olefins such as those derived from butene, hexene, and / or octene) may be present in the ethylene copolymer from a low of 2, 2.5, 3, 3.5, 4, 4.5, 5, or 6% by weight to a high of 3, 4, 5, 6, 7, 8, 9, 10, 15, or 20% by weight, ranging from the low value to the contemplated high value (provided the high value is greater than the low value).

[0051] While several suitable comonomers are known for ethylene-, propylene-, or other α-olefin-based copolymers, various embodiments contemplate other α-olefin comonomers. For example, the α-olefin comonomer may be linear or branched, and two or more comonomers may be used if desired. Examples of suitable comonomers include linear C3-C20 α-olefins (such as butene, hexene, and octene, as previously mentioned) and α-olefins having one or more C1-C3 alkyl branched or aryl groups. Examples include propylene; 3-methyl-1-butene; 3,3-dimethyl-1-butene; 1-pentene; 1-pentene having one or more methyl, ethyl, or propyl substituents; 1-hexene having one or more methyl, ethyl, or propyl substituents; 1-heptene having one or more methyl, ethyl, or propyl substituents; 1-octene having one or more methyl, ethyl, or propyl substituents; 1-nonene having one or more methyl, ethyl, or propyl substituents; ethyl-, methyl-, or dimethyl-substituted 1-decene; 1-dodecene; and styrene. The above list of comonomers is merely illustrative and not intended to be limiting. In some embodiments, the comonomers include propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, and styrene.

[0052] In certain embodiments, the polymer can comprise or be (in accordance with those described above) an ethylene copolymer. The ethylene copolymer can be produced by gas, slurry, or solution phase polymerization, with some particularly preferred ethylene copolymers being produced by gas or slurry phase polymerization. A particular example is linear low density polyethylene (LLDPE), a copolymer of ethylene and one or more α-olefins, polymerized in the presence of one or more single-site catalysts, such as one or more Ziegler-Natta catalysts, one or more metallocene catalysts, and combinations thereof. Such LLDPEs have viscosity profiles of 0.900, 0.905, 0.907, 0.910 g / cm. ３from a low concentration of 0.920, 0.925, 0.930, 0.935, 0.940, or 0.945 g / cm ３ and high concentrations. LLDPE can be distinguished from the LDPEs described above in several respects, many of which are well known in the art, including the degree of branching (often little, if any) in the produced polymer; it is noted that LLDPE has substantially less long chain branching. In certain embodiments, the polymer of the polymer composition is or comprises a metallocene-catalyzed LLDPE (mLLDPE). In yet other embodiments, the polymer of the polymer composition is or comprises a Ziegler-Natta-catalyzed LLDPE (or ZN-LLDPE).

[0053] The density of the polymer may also be, in some embodiments, from 0.905 to 0.945 g / cm ３ In the range of, for example, 0.905, 0.907, 0.908, 0.910, 0.911, 0.912, 0.913, 0.914, or 0.915 g / cm ３ from the lower value of 0.916, 0.917, 0.918, 0.919, 0.920, 0.924, 0.926, 0.930, 0.935, 0.940, or 0.945 g / cm ３ to any higher value, the range being from the lower to higher values ​​contemplated herein (e.g., 0.910 to 0.925 or 0.935 g / cm ３ , for example 0.912 to 0.925 or 0.915 to 0.918 g / cm ３ In yet another embodiment, the polymer has a density of 0.945 g / cm ３ to 0.970 g / cm ３ It may also be of higher density (eg HDPE) having a density in the range

[0054] Furthermore, the rheological properties of the polymer can influence the processing aid composition to form the molding. Generally, it is preferred that the PPA composition be used in polymers having a melt index (MI or I2 measured at 190°C under a 2.16 kg load according to ASTM D1238) of 1.5 g / 2.0 min or less, preferably 2.5 g / 3.0 min or less, such as in the range of 0.1, 0.2, or 0.5 g / 10 min to 1.0, 1.2, 5.0, 10, 2.5, 10, 4.0, or 5.0 g / 10 min. The melt index ratio (MIR) (MIR is defined herein as the ratio of the high load melt index (HLMI) (measured per ASTM D1238 at 190°C under a load of 21.6 kg) to the melt index, or HLMI / MI), in some embodiment polymers may have an MIR generally within the range of 10, 12, or 15 to 19, 20, 21, 22, 25, 27, 30, 35, 40, 45, 50, 60, 65, 70, 75, 80, 85, 90, 95, or 100. Optionally, the MI in such polymers can be less than 1.5 g / 10 min, such as 1.0 g / 10 min or less (e.g., 0.1, 0.2, or 0.5 g / 10 min to 1.0; or 1.1, 1.2, 1.3, 1.4, or less than 1.5 g / 10 min).

[0055] The LLDPE is preferably at least one selected from the group consisting of Ziegler-Natta catalyst LLDPE and metallocene catalyst LLDPE, with metallocene catalyst LLDPE being particularly preferred.

[0056] The thermoplastic resin (B) may be crystalline or non-crystalline. When the thermoplastic resin (B) is crystalline, it preferably has a melting point of 80 to 300°C, more preferably 100 to 200°C. The non-crystalline thermoplastic resin (B) preferably has a processing temperature approximately equal to that of a crystalline thermoplastic resin (B) having a specified melting point range.

[0057] In the thermoplastic resin composition of the present disclosure, the resin (A) is dispersed in the thermoplastic resin (B), that is, the thermoplastic resin composition of the present disclosure forms a sea-island structure in which the thermoplastic resin (B) forms a sea and the resin (A) forms islands.

[0058] In the thermoplastic resin composition of the present disclosure, the dispersed particle diameter of the resin (A) is 1 to 100 μm. Within this range, good processability can be obtained. The lower limit is preferably 5 μm or more, and the upper limit is preferably 80 μm or less, more preferably 50 μm or less, even more preferably 40 μm or less, and particularly preferably 30 μm or less.

[0059] When the dispersed particle size of the resin (A) is 10 μm or more, the melt fracture disappearance time is shortened. Therefore, from the viewpoint of the melt fracture disappearance time, the dispersed particle size of the resin (A) is preferably 10 to 100 μm, more preferably 15 to 50 μm, and even more preferably 30 to 50 μm.

[0060] When the dispersed particle diameter of the resin (A) is 50 μm or less, the amount of die buildup (DBU) that occurs is reduced. Therefore, from the viewpoint of suppressing DBU, the dispersed particle diameter of the resin (A) is preferably 1 to 50 μm, and more preferably 5 to 30 μm.

[0061] The dispersed particle diameter of the resin (A) can be measured by the following method. (1) Using a microtome, a thermoplastic resin composition in which the resin (A) is dispersed in the thermoplastic resin (B) is cut perpendicular to the extrusion direction to a thickness of approximately 30 μm, and 10 samples are collected. Each of the collected samples is heated to 190°C at a heating rate of 10°C / min and then left to melt for 10 minutes. (2) The molten thermoplastic resin composition is observed under a polarizing microscope (Nikon ECLIPSE LV100N POL (camera: Nikon DS-Fi2), magnification: 200x). The captured images are analyzed using analysis software (NIS-Elements D) to measure the particle diameter. One image is taken for each sample, for a total of 10 images, and the average particle diameter of the dispersed particles in the images is taken as the dispersed particle diameter. If the particles are not circular, the major axis is taken as the particle diameter.

[0062] The dispersed particle size of the resin (A) can be adjusted, for example, by the mixing conditions. Specifically, the dispersed particle size becomes smaller under conditions of strong shear force on the target object, and becomes larger under conditions of weak shear force on the target object. As a method for adjusting the dispersed particle size of the resin (A) to a range preferable for improving processability, for example, the method for producing the thermoplastic resin composition of the present disclosure described below can be mentioned.

[0063] The thermoplastic resin composition of the present disclosure may be a masterbatch, a composition mixed with a masterbatch, or a composition not mixed with a masterbatch. However, from the viewpoint of obtaining better processability, a masterbatch or a composition mixed with a masterbatch is preferred.

[0064] When the thermoplastic resin composition of the present disclosure is a masterbatch, it is particularly useful as a processing aid for thermoplastic resins (particularly polyolefin resins).

[0065] When the thermoplastic resin composition of the present disclosure is a masterbatch, the melt flow rate (MFR) of the masterbatch is preferably 0.1 g / 10 min or more, more preferably 0.5 g / 10 min or more, even more preferably 1 g / 10 min or more, still more preferably 1.5 g / 10 min or more, and is preferably 100 g / 10 min or less, more preferably 50 g / 10 min or less, even more preferably 30 g / 10 min or less, still more preferably 20 g / 10 min or less, and particularly preferably 10 g / 10 min or less. Within the above ranges, the effect of improving processability is more favorable.

[0066] When the thermoplastic resin composition of the present disclosure is a masterbatch, the content of the resin (A) is preferably 1% by mass or more, more preferably 3% by mass or more, even more preferably 5% by mass or more, particularly preferably 8% by mass or more, and is preferably 80% by mass or less, more preferably 50% by mass or less, even more preferably 40% by mass or less, particularly preferably 30% by mass or less.

[0067] When the thermoplastic resin composition of the present disclosure is a masterbatch, the mass ratio of the thermoplastic resin (B) to the resin (A) (thermoplastic resin (B):resin (A)) is preferably 99:1 to 1:99. The mass ratio is more preferably 97:3 to 50:50, even more preferably 95:5 to 60:40, and particularly preferably 92:8 to 70:30.

[0068] When the thermoplastic resin composition of the present disclosure is a masterbatch, the total content of the thermoplastic resin (B) and the resin (A) is preferably 80% by mass or more, more preferably 90% by mass or more, even more preferably 95% by mass or more, and particularly preferably 100% by mass.

[0069] When the thermoplastic resin composition of the present disclosure is a composition mixed with a masterbatch or a composition not mixed with a masterbatch, the content of the resin (A) is preferably 0.001% by mass or more, more preferably 0.08% by mass or more, even more preferably 0.1% by mass or more, and is preferably 5% by mass or less, more preferably 3% by mass or less, even more preferably 2% by mass or less, and particularly preferably 1.0% by mass or less.

[0070] When the thermoplastic resin composition of the present disclosure is a composition mixed with a masterbatch, the composition is preferably a thermoplastic resin composition containing a masterbatch containing the resin (A) and the thermoplastic resin (B), and a thermoplastic resin (C). This provides good processability. In particular, good extrusion processability can be obtained even during long-run molding. Furthermore, the storage stability of the extrusion-processed product is also excellent.

[0071] The thermoplastic resin (C) may be the same as the thermoplastic resin (B), and the preferred forms are also the same. When the thermoplastic resin composition of the present disclosure is a composition mixed with a masterbatch, the thermoplastic resin (B) and the thermoplastic resin (C) may be the same or different.

[0072] The thermoplastic resin composition of the present disclosure is preferably substantially free of fluorine. "Substantially free of fluorine" means that the fluorine content in the processing aid is 10 ppm or less (preferably 1 ppm or less, more preferably 0.1 ppm or less). It is particularly preferable that the processing aid of the present disclosure is fluorine-free (the fluorine content is 0 mass %).

[0073] The moisture content of the processing aid of the present disclosure is preferably 1.0% by mass or less, more preferably 0.5% by mass or less, even more preferably 0.2% by mass or less, and most preferably 0.1% by mass or less. The lower limit is not particularly limited, and may be 0% by mass.

[0074] In this specification, the water content is measured by the following method. The mass of the thermoplastic resin composition of the present disclosure is measured before and after heating at 130°C for 24 hours, and calculated according to the following formula. A sample is taken three times, and the mass is calculated for each sample, and the average value is calculated and adopted. Water content (mass%) = [(mass (g) of thermoplastic resin composition before heating) - (mass (g) of thermoplastic resin composition after heating)] / (mass (g) of thermoplastic resin composition before heating) x 100

[0075] The method for obtaining a thermoplastic resin composition having a moisture content within the above range is not particularly limited. For example, a thermoplastic resin composition may be prepared under dry conditions using materials with a low moisture content, or a thermoplastic resin composition may be prepared using ordinary materials and conditions, and then the moisture may be removed by heat treatment or the like.

[0076] The thermoplastic resin composition of the present disclosure may contain components other than the resin (A), the thermoplastic resin (B), and the thermoplastic resin (C). Examples of the other components include a synergist that is at least one selected from the group consisting of a polyol having a melting point of 80°C or less, polycaprolactone, silicone, and a polyamide-polyether block copolymer.

[0077] The melting point of the polyol may be 80° C. or lower, preferably 75° C. or lower, more preferably 70° C. or lower, and even more preferably 68° C. or lower, and is preferably 10° C. or higher, more preferably 20° C. or higher, and even more preferably 25° C. or higher. Within the above ranges, the effect of improving processability is better.

[0078] The polyol may be, for example, A[(OR １１ ) ｘ OR １２ ] ｙ where A is typically an alkylene having one or more ether linkages, y is 2 or 3, and (OR １１ ) ｘ is an oxyalkylene group OR １１ is a poly(oxyalkylene) chain having a plurality (x) of R １１ are each independently C ２ ~C ５ alkylene, and in some embodiments, C ２ ~C ３ alkylene, and R １２ is hydrogen, alkyl, aryl, arylalkenyl, alkylarylenyl, —C(O)-alkyl, —C(O)-aryl, —C(O)-arylalkenyl or —C(O)-alkylarylenyl, and —C(O)— is OR １２ is bonded to O in the formula (I), and x is 10 to 230,000.

[0079] The polyol is R １１ But -CH ２ CH ２ -, or a homopolymer of poly(oxypropylene) where R １１ But, -C ３ H ６ -, and the like.

[0080] The polyols may contain randomly distributed oxyalkylene groups (e.g., copolymers of -OC ２ H ４ - and -OC ３ H ６-units), or alternating blocks of repeating oxyalkylene groups (e.g., (-OC ２ H ４ -) ａ１ Block and (-OC ３ H ６ -) ｂ１ It may also be a chain having a polymer containing blocks, where a1+b1 is from 10 to 230,000.

[0081] In some embodiments of the above polyols, A is ethylene, —CH ２ -CH(-)-CH ２ - (derived from glycerol), CH ３ CH ２ C(CH ２ -) ３ (derived from 1,1,1-trimethylolpropane), poly(oxypropylene), -CH ２ CH ２ -O-CH ２ CH ２ - or -CH ２ CH ２ -O-CH ２ CH ２ -O-CH ２ CH ２ - and R １２ is hydrogen, methyl, butyl, phenyl, benzyl, acetyl, benzoyl or stearyl.

[0082] The polyol is a dicarboxylic acid and A[(OR １１ ) ｘ２ OR １２ ] ｙ２ A polyester prepared from a poly(oxyalkylene) polymer represented by the formula: １１ and x2 are as defined above, R １２ is hydrogen and y2 is 2.

[0083] The polyols may be used alone or in combination of two or more. From the viewpoint of excellent effect of improving processability, polyethylene glycol and polyethylene oxide are preferred, and polyethylene glycol is particularly preferred.

[0084] The number average molecular weight (Mn) of the polyethylene glycol is preferably 1,000 or more, more preferably 3,000 or more, even more preferably 5,000 or more, and is preferably 50,000 or less, more preferably 45,000 or less, even more preferably 40,000 or less. Within the above ranges, the effect of improving processability is better. In this specification, the number average molecular weight is calculated from the hydroxyl value measured in accordance with JIS K0070.

[0085] The viscosity average molecular weight (Mv) of the polyethylene oxide is preferably 100,000 or more, more preferably 120,000 or more, even more preferably 140,000 or more, and preferably 10,000,000 or less, more preferably 1,600,000 or less, even more preferably 500,000 or less. Within the above ranges, the effect of improving processability is better. In this specification, the viscosity average molecular weight is calculated as follows: Using an Ostwald viscometer, the specific viscosity ηsp of aqueous solutions of various polymer concentrations c (g / dl) in pure water is measured at 35°C, and [η] is calculated by extrapolating the polymer concentration c to 0 based on the relationship between the reduced viscosity (ηsp / c) obtained by dividing the specific viscosity by the polymer concentration and the polymer concentration c. [η] is inserted into the following formula to calculate the viscosity average molecular weight M: Formula: [η] = 6.4 × 10 －５ M ０．８２

[0086] The polycaprolactone may be a homopolymer of ε-caprolactone or a modified polycaprolactone, such as one modified by ring-opening polymerization of ε-caprolactone in the presence of 1,4-butanediol or the like, or one modified at the end of the polymer with an ether or ester group or the like.

[0087] The weight average molecular weight (Mw) of the polycaprolactone is preferably 2,000 or more, more preferably 10,000 or more, even more preferably 25,000 or more, and is preferably 100,000 or less, more preferably 95,000 or less, even more preferably 90,000 or less. Within the above ranges, the effect of improving processability is more excellent. In this specification, the weight average molecular weight is measured in terms of polystyrene by gel permeation chromatography (GPC).

[0088] The melting point of the polycaprolactone is preferably 80° C. or lower, more preferably 75° C. or lower, even more preferably 70° C. or lower, and particularly preferably 68° C. or lower, and is preferably 10° C. or higher, more preferably 20° C. or higher, and even more preferably 45° C. or higher. Within the above ranges, the effect of improving processability is more favorable.

[0089] Said silicones can in principle be all organosilicon compounds known to those skilled in the art under the term silicone polymer. A suitable definition of silicone can be found in Winnacker / Kuchler: "Chemische Technik" [Chemical Technology], R. Dittmeyer, W. Keim, G. Kreysa, A. Oberholz (eds.), Volume 5: "Organische Zwischenverbindungen, Polymere" [Organic Intermediates, Polymers], Chapter: "Silicones", Wiley-VCH, Weinheim, 2005.

[0090] Silicone can be substituted or unsubstituted linear oligo- or polydiorganosiloxane, branched silicone polymer, silicone resin or crosslinked silicone polymer.Of course, mixtures of various silicone polymers can also be used.As mentioned above, silicone-containing copolymers can also be used, such as polyether functional silicone, silicone containing urea or urethane unit, or silicone block copolymers with organic polymers.For the purpose of better compatibility, it is particularly preferred to use high molecular weight polydiorganosiloxanes, which can also contain non-silicone components, such as fillers such as finely divided silica, chalk, talc and sheet silicate.

[0091] Preferably, the silicone polymer corresponds to formula A, where R １３ ３ SiO １／２ ] ａ２ [SiR １３ ２ O ２／２ ] ｂ２ [R １３ SiO ３／２ ] ｃ２ [SiO ４／２ ] ｄ２ , where R １３ is hydrogen, —OH, or an unsubstituted or substituted C1 to C18 hydrocarbon residue; a2, b2, c2, and d2 each represent 0 or an integer, and a2+b2+c2+d2 represents an integer of 5 to 15,000.

[0092] C1 to C18 hydrocarbon residue R １３Examples of alkyl residues are alkyl residues such as methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, hexyl residues such as n-hexyl, heptyl residues such as n-heptyl, octyl residues such as n-octyl and isooctyl, nonyl residues such as n-nonyl, decyl residues such as n-decyl, cycloalkyl residues such as cyclopentyl, cyclohexyl, 4-ethylcyclohexyl and cycloheptyl, norbornyl and methylcyclohexyl. Among the alkyl residues, C1 to C6 residues are preferred, such as methyl and ethyl residues, especially methyl.

[0093] R １３ Examples of unsaturated C1 to C18 hydrocarbon residues R are also unsaturated C1 to C18 hydrocarbon residues, such as alkenyl residues, for example vinyl, 2-propen-2-yl, allyl, 3-buten-1-yl, 5-hexen-1-yl, 10-undecen-1-yl, and cycloalkenyl residues (2-cyclohexenyl, 3-cyclohexenyl, cyclopentadienyl, 2-(cyclohex-3-en-1-yl)ethyl); aryl residues, for example phenyl, biphenylyl, and naphthyl; alkaryl residues, for example o-, m-, and p-tolyl, and phenethyl (2-phenylethyl, 1-phenylethyl) and aralkyl residues, for example benzyl. Preferred unsaturated C1 to C18 hydrocarbon residues R １３ are vinyl and phenyl residues.

[0094] residue R １３ Examples of substituted hydrocarbon residues as are halogenated hydrocarbons, such as the chloromethyl, 3-chloropropyl, 3-bromopropyl, 3,3,3-trifluoropropyl and 5,5,5,4,4,3,3-heptafluoropentyl residues, as well as the chlorophenyl, dichlorophenyl and trifluorotolyl residues.

[0095] residue R１３ is preferably bonded to the silicone polymer of formula A via an Si—C bond, but can also be bonded to the silicone polymer via an oxygen atom —O—.

[0096] R １３ preferably has 1 to 6 carbon atoms. The ethyl, phenyl, vinyl and methyl residues are particularly preferred.

[0097] Preferably, a2+b2+c2+d2 means a number of at least 10, more preferably at least 100, particularly preferably at least 1000 and at most 15000, more preferably at most 10000, particularly preferably at most 7000.

[0098] Preferably, c2+d2<0.1*(a2+b2+c2+d2), in particular c2+d2<0.05*(a2+b2+c2+d2).

[0099] Preferably, all residues R １３ At least 50%, more preferably at least 70%, and particularly preferably at least 80% of these groups represent methyl residues.

[0100] In principle, all silicone polymers corresponding to formula (A) can be used, but preference is given to silicone polymers having a dynamic viscosity of more than 1000 mPa.s, preferably measured according to DIN EN ISO 3219:1994 and DIN 53019 using an Anton Paar "MCR 302" rheometer with a 2° opening angle, 50 mm diameter plate-cone system (cone CP50-2), a measuring temperature of 25.00°C ± 0.05°C, and a shear rate of 1 sec-1.

[0101] Among silicones, silicone polymers having very high molecular weights, such as UHMW polysiloxanes (ultra-high molecular weight; described in K. J. Ryan et al., Journal of Vinyl & Additive Technology, March 2000, Vol. 6, No. 1, pp. 7-19), may be used.

[0102] The degree of polymerization of UHMW polysiloxanes ranges from >1000 to about 14000, which corresponds to a number average molecular weight between 74 kg / mol and 1000 kg / mol.

[0103] Typical UHMW polysiloxanes preferably have a dynamic viscosity between 10 kPa.s and 50 kPa.s, preferably between 15 kPa.s and 30 kPa.s, measured with an airborne rotational rheometer according to DIN EN ISO 3219:1994 and DIN 53019, where a plate-plate system (25 mm diameter) with a measuring gap of 0.5 mm is used. The measurement temperature is 25.00°C + / - 0.1°C. The shear rate gradient is 0.1 sec －１ The viscosity reading represents the arithmetic mean of three individual measurements carried out independently.

[0104] Of the above UHMW polysiloxanes, high molecular weight polydimethylsiloxanes having a dynamic viscosity between 1 kPa.s and 50 kPa.s, preferably between 10 and 40 kPa.s, and particularly preferably between 15 and 30 kPa.s (preferably measured by the method described above) are particularly preferred, as they are inexpensive and effective.

[0105] Examples of the UHMW polysiloxane include commercially available UHMW polysiloxanes such as MULTIBASE (registered trademark) MB50-001 and MULTIBASE (registered trademark) MB50-002 manufactured by DuPont, and GENIOPLAST (registered trademark) PELLET S, GENIOPLAST (registered trademark) PELLET P Plus, GENIOPLAST (registered trademark) PE50S08, GENIOPLAST (registered trademark) PP50S12 manufactured by Wacker Asahi Kasei Silicones, and mixtures thereof, with MB50-002 and GENIOPLAST (registered trademark) PELLET S being preferred.

[0106] Silicone polymers are commercially available as ready-to-use pellets / granules or masterbatches, which can be mixed into, for example, thermoplastic granules prior to their further processing.

[0107] The polyamide-polyether block copolymer is a copolymer having a polyamide block and a polyether block in the polymer backbone. In the present disclosure, such a block copolymer having a polyamide block and a polyether block may also be referred to as a "polyamide / polyether block copolymer." It may also be abbreviated as a "PEBA copolymer" or "PEBA." In some embodiments of the present disclosure, the PEBA copolymer may be represented by the following general formula:

[0108] where PA is the polyamide block, PE is the polyether block, and p is the length of the PEBA copolymer, representing the total number of polyamide and polyether blocks. In some embodiments of the present disclosure, the PEBA copolymer can be represented by the following general formula:

[0109] where EG is a first unspecified terminal group, B is an unspecified bridging group, EG ＊ is a second unspecified end group, and EG, B and EG ＊ is determined by the synthesis method used to produce the PEBA copolymer, where n2 represents the length of the polyamide block, x3 represents the length of the amide component within the polyamide block, m1 represents the length of the poly(ether) block, y3 represents the length of the ether component within the poly(ether) block, and p represents the length of the PEBA copolymer and the total number of polyamide and polyether blocks. In some embodiments of the present disclosure, the PEBA copolymer can be represented by the following general formula:

[0110] Here, n2 represents the length of the polyamide block, x3 represents the length of the amide component in the polyamide block, m1 represents the length of the poly(ether) block, y3 represents the length of the ether component in the poly(ether) block, p represents the length of the PEBA copolymer, and represents the total number of polyamide and polyether blocks.

[0111] The polyamide blocks in the PEBA copolymer are derived from polyamide-12 (PA-12), polyamide-11 (PA-11), polyamide-6 (PA-6), or polyamide-66 (PA-66).

[0112] The weight average molecular weight (e.g., Mw and Mn) of the PEBA copolymer can be measured, for example, by gel permeation chromatography (i.e., size exclusion chromatography) using narrow molecular weight polymer standards using techniques known in the art.

[0113] In embodiments, the number average molecular weight Mn of the polyamide blocks in the PEBA copolymer is from about 100 to about 15,000 g / mol, or from about 300 to about 15,000 g / mol, or from about 600 to about 10,000 g / mol, or from about 600 to about 5,000 g / mol. The number average molecular weight Mn of the polyether blocks in the PEBA copolymer is from about 100 to about 15,000 g / mol, from about 100 to about 10,000 g / mol, from about 100 to about 6,000 g / mol, from about 100 to about 3,000 g / mol, from about 200 to about 6,000 g / mol, from about 200 to about 3,000 g / mol, from about 250 to about 2,000 g / mol, from about 750 to about 3,500 g / mol, or from about 1,000 to about 3,000 g / mol.

[0114] The PEBA copolymer has a number average molecular weight, Mn, of from 10,000 to 500,000 g / mol, including any subrange and any number within this range. For example, in embodiments of the present disclosure, the PEBA copolymer has a number average molecular weight Mn of from 10,000 to 400,000 g / mol, or from 10,000 to 300,000 g / mol, or from 10,000 to 250,000 g / mol, or from 15,000 to 300,000 g / mol, or from 20,000 to 300,000 g / mol, or from 15,000 to 200,000 g / mol, or from 20,000 to 200,000 g / mol, or from 30,000 to 250,000 g / mol, or from about 25,000 to about 75,000 g / mol, or from about 50,000 to about 75,000 g / mol, or from about 100,000 to about 150,000 g / mol. The PEBA copolymer has a number average molecular weight Mn of at least 10,000 g / mol, at least 20,000 g / mol, at least 25,000 g / mol, greater than 25,000 g / mol, at least 30,000 g / mol, greater than 30,000 g / mol, at least 35,000 g / mol, greater than 35,000 g / mol, at least 50,000 g / mol, or greater than 50,000 g / mol.

[0115] In embodiments, the weight average molecular weight M of the PEBA copolymer is from 25,000 to 500,000 g / mol, including subranges and any number within this range. For example, in embodiments of the present disclosure, the weight average molecular weight M of the PEBA copolymer is from about 100,000 to about 250,000 g / mol, or from about 100,000 to about 150,000 g / mol, or from about 125,000 to about 150,000 g / mol. The polyamide and polyether blocks within the PEBA copolymer can be randomly distributed.

[0116] The PEBA copolymer may comprise polyamide blocks and polyether blocks, with the polyamide blocks comprising at least 50% by weight of the copolymer. The PEBA copolymer may comprise polyamide blocks and polyether blocks, with the polyether blocks comprising at least 50% by weight of the copolymer. Further, the PEBA copolymer may comprise polyamide blocks and polyether blocks, with the molar ratio of polyamide blocks to polyether blocks ranging from 1:3 to 3:1, or from 1:2 to 2:1, or from 3:2 to 1:3, or from 2:3 to 3:1, or about 1:1.

[0117] PEBA copolymers having polyamide and polyether blocks can be prepared by reacting the polyamide and polyether block precursors. For example, lactams, polyether diols, and chain-limiting diacids can be reacted together in the presence of a small amount of water to obtain PEBA copolymers having polyamide and polyether blocks of variable length and statistically randomly distributed within the block copolymer chain. The polyether blocks can be derived from poly(oxyethylene), poly(oxypropylene), or poly(tetramethylene ether) glycol, each of which can be naturally co-condensed with a polyamide block containing carboxylic acid chain ends. A chain-limiting agent can also be present during the polycondensation reaction to provide PEBA copolymers having polyamide and polyether blocks randomly distributed within the block copolymer. The polyether blocks can be derived from poly(oxyethylene), poly(oxypropylene), or poly(tetramethylene ether) glycol, which are first converted to polyether diamines by amination and then co-condensed with a polyamide block containing carboxylic acid chain ends. A chain limiter may also be present during the polycondensation reaction to provide a PEBA copolymer containing polyamide blocks and polyether blocks randomly distributed within the block copolymer. The polyether blocks may be derived from poly(oxyethylene), also known as polyethylene glycol (PEG). The polyether blocks may be derived from poly(oxypropylene), also known as polypropylene glycol (PPG). The polyether blocks may be derived from poly(tetramethylene ether) glycol (PTMG), also known as polytetramethylene oxide (PTMEO) or polytetrahydrofuran (PTHF).

[0118] The PEBA copolymer comprises i) polyamide blocks selected from polyamide-12 (PA-12), polyamide-11 (PA-11), polyamide-6 (PA-6), or mixtures thereof, and ii) polyether blocks selected from polyethylene glycol (PEG), polypropylene glycol (PPG), polytetrahydrofuran (PTHF), or mixtures thereof.

[0119] The PEBA copolymer comprises i) a polyamide block selected from polyamide-12 (PA-12), polyamide-11 (PA-11), polyamide-6 (PA-6), or a mixture thereof, and ii) a polyether block that is polyethylene glycol (PEG). In one embodiment of the present disclosure, the PEBA copolymer comprises i) a polyamide block that is polyamide-12 (PA-12), and ii) a polyether block that is polyethylene glycol (PEG).

[0120] The PEBA copolymer contains 10 to 20 polyamide blocks and 10 to 20 polyether blocks.

[0121] The PEBA copolymer contains only one type of polyamide block and one type of polyether block.

[0122] The PEBA copolymer comprises i) a polyamide block that is polyamide-12 (PA-12), and ii) a polyether block that is polyethylene glycol (PEG), wherein the polyamide-12 block comprises about 30% to 70% by weight of the copolymer and the polyethylene glycol block comprises about 70% to 30% by weight of the copolymer.

[0123] The PEBA copolymer comprises i) a polyamide block that is polyamide-12 (PA-12), and ii) a polyether block that is polyethylene glycol (PEG), wherein the polyamide-12 block comprises about 40% to 60% by weight of the copolymer and the polyethylene glycol block comprises about 60% to 40% by weight of the copolymer.

[0124] The PEBA copolymer comprises i) a polyamide block that is polyamide-12 (PA-12) and ii) a polyether block that is polyethylene glycol (PEG), where the polyamide-12 block represents about 45% by weight of the copolymer and the polyethylene glycol block represents about 55% by weight of the copolymer.

[0125] The PEBA copolymer comprises i) 10 to 20 polyamide blocks that are polyamide-12 (PA-12), and ii) 10 to 20 polyether blocks that are polyethylene glycol (PEG).

[0126] The PEBA copolymer comprises i) a polyamide block that is polyamide-12 (PA-12), and ii) a polyether block that is polyethylene glycol (PEG), and has a number average molecular weight Mn of about 25,000 to about 75,000 g / mol.

[0127] The PEBA copolymer comprises i) a polyamide block that is polyamide-12 (PA-12) and ii) a polyether block that is polyethylene glycol (PEG), and has a number average molecular weight Mn of about 50,000 to about 75,000 g / mol. The PEBA copolymer comprises i) a polyamide block that is polyamide-12 (PA-12) and ii) a polyether block that is polyethylene glycol (PEG), and has a number average molecular weight Mn of about 66,100 g / mol.

[0128] The PEBA copolymer comprises i) a polyamide block that is polyamide-12 (PA-12), and ii) a polyether block that is polyethylene glycol (PEG), and has a weight average molecular weight Mw of about 100,000 to about 150,000 g / mol.

[0129] The PEBA copolymer comprises i) a polyamide block that is polyamide-12 (PA-12), and ii) a polyether block that is polyethylene glycol (PEG), and has a weight average molecular weight Mw of about 125,000 to about 150,000 g / mol.

[0130] The PEBA copolymer comprises i) a polyamide block which is polyamide-12 (PA-12) and ii) a polyether block which is polyethylene glycol (PEG), and has a weight average molecular weight Mw of about 134,000 g / mol.

[0131] In one embodiment of the present disclosure, the PEBA copolymer comprises i) a polyamide block that is polyamide-6 (PA-6) and ii) a polyether block that is polyethylene glycol (PEG), wherein the polyamide-6 block represents about 30% to 60% by weight of the copolymer and the polyethylene glycol block represents about 70% to 40% by weight of the copolymer.

[0132] The PEBA copolymer comprises i) a polyamide block that is polyamide-6 (PA-6) and ii) a polyether block that is polyethylene glycol (PEG), where the polyamide-6 block represents about 50% to 35% by weight of the copolymer and the polyethylene glycol block represents about 50% to 65% by weight of the copolymer.

[0133] The PEBA copolymer comprises i) 10 to 20 polyamide blocks that are polyamide-6 (PA-6), and ii) 10 to 20 polyether blocks that are polyethylene glycol (PEG).

[0134] The PEBA copolymer comprises i) a polyamide block that is polyamide-11 (PA-11), and ii) a polyether block that is polyethylene glycol (PEG). In one embodiment of the present disclosure, the PEBA copolymer comprises i) a polyamide block that is polyamide-12 (PA-12), and ii) a polyether block that is polytetrahydrofuran (PTHF).

[0135] The PEBA copolymer comprises i) a polyamide block that is polyamide-12 (PA-12), and ii) a polyether block that is polytetrahydrofuran (PTHF), wherein the polyamide-12 block represents about 75% to 10% by weight of the copolymer and the polytetrahydrofuran block represents about 25% to 90% by weight of the copolymer.

[0136] The PEBA copolymer comprises i) a polyamide block that is polyamide-12 (PA-12), and ii) a polyether block that is polytetrahydrofuran (PTHF), wherein the polyamide-12 block represents about 80% to 60% by weight of the copolymer and the polytetrahydrofuran block represents about 20% to 40% by weight of the copolymer.

[0137] The PEBA copolymer comprises i) a polyamide block that is polyamide-12 (PA-12), and ii) a polyether block that is polytetrahydrofuran (PTHF), wherein the polyamide-12 block represents about 40% to 60% by weight of the copolymer and the polytetrahydrofuran block represents about 60% to 40% by weight of the copolymer.

[0138] The PEBA copolymer comprises i) a polyamide block that is polyamide-12 (PA-12), and ii) a polyether block that is polytetrahydrofuran (PTHF), where the polyamide-12 block represents about 30% to 10% by weight of the copolymer and the polytetrahydrofuran block represents about 70% to 90% by weight of the copolymer. The PEBA copolymer comprises i) 10 to 20 polyamide blocks that are polyamide-12 (PA-12), and ii) 10 to 20 polyether blocks that are polytetrahydrofuran (PTHF).

[0139] The PEBA copolymer comprises i) a polyamide block that is polyamide-12 (PA-12) and ii) a polyether block that is polytetrahydrofuran (PTHF), and has a number average molecular weight Mn of about 25,000 to about 75,000 g / mol. The PEBA copolymer comprises i) a polyamide block that is polyamide-12 (PA-12) and ii) a polyether block that is polytetrahydrofuran (PTHF), and has a number average molecular weight Mn of about 40,000 to about 60,000 g / mol. In an embodiment of the present disclosure, the PEBA copolymer comprises i) a polyamide block that is polyamide-12 (PA-12) and ii) a polyether block that is polytetrahydrofuran (PTHF), and has a number average molecular weight Mn of about 50,000 g / mol.

[0140] The PEBA copolymer contains i) a polyamide block that is polyamide-6 (PA-6), and ii) a polyether block that is polytetrahydrofuran (PTHF). The PEBA copolymer contains i) a polyamide block that is polyamide-11 (PA-11), and ii) a polyether block that is polytetrahydrofuran (PTHF). The PEBA copolymer is a commercially available elastomer sold under the trade name PEBAX®.

[0141] The PEBA copolymer is a commercially available elastomer selected from the group consisting of: PEBAX 2533 SA 01, PEBAX 2533 SA 01 MED, PEBAX 2533 SD 02, PEBAX 3533 SA 01, PEBAX 3533 SA 01 MED, PEBAX 3533 SP01, PEBAX 4011, PEBAX 4033 SA 01, PEBAX 4033 SA 01 MED, PEBAX 4033 SP01, PEBAX 4533 SA 01, PEBAX 4533 SA 01 MED, PEBAX 4533 SP01, PEBAX 5513 SA 01, PEBAX 5513 SP01, PEBAX 5533 SA 01, PEBAX 5533 SA 01 MED, PEBAX 5533 SN 70 BLACK, PEBAX 5533 SP01, PEBAX SA 01, PEBAX 6333 SA 01 MED, PEBAX SP01, PEBAX 6333 SP01, PEBAX 6333 SA 01, PEBAX, PEBAX 3533 SA 01, PEBAX 3533 SA 01 MED, PEBAX 3533 SP01, PEBAX 4011 SA 01, PEBAX 4033 SA 01 MED, PEBAX 4033 SP01, PEBAX 4033 SA 01 MED, PEBAX Clear 2533, PEBAX ES 2533 UV, PEBAX MH 2533, PEBAX MH2030, PEBAX MV 5513 SA 01, PEBAX MV 5513 SA 01 MED, PEBAX MV 5533 SP01, PEBAX MV 5533, PEBAX MV 5533 SP01, PEBAX RNEW (registered trademark) 30R51 SA 01, PEBAX RNEW 35R53 SP01, PEBAX PEBAX RNEW 70R53 SP01, PEBAX RNEW 55R53 SP01, PEBAX RNEW 63R53 SP01, PEBAX RNEW 70R53 SP01, PEBAX RNEW 70R53 SP01, PEBAX, PEBAX RNEW 72R53 SP01, PEBAX RNEW 80R53 SP 02 and mixtures thereof.The PEBA copolymer is a commercially available elastomer sold under the trade name VESTAMID® or VESTAMID E.

[0142] The PEBA copolymer is a commercially available elastomer selected from the group consisting of VESTAMID D, VESTAMID DX, VESTAMID E, VESTAMID EX, VESTAMID Care, VESTAMID Care ML, VESTAMID Care ME, VESTAMID Care ME-B, VESTAMID L, VESTAMID LX, VESTAMID NRG, VESTAMID Terra, VESTAMID X, and mixtures thereof, with Pebax MV1072 being preferred.

[0143] The PEBA copolymer can be used in the form of a semi-solid or viscous liquid, or as a powder, pellets, or granules.

[0144] Other components that can be used include, for example, anti-adhesion agents; ultraviolet absorbers; flame retardants; reinforcing materials such as glass fiber and glass powder; stabilizers such as minerals and flakes; lubricants such as silicone oil and molybdenum disulfide; pigments such as titanium dioxide and red iron oxide; conductive agents such as carbon black; impact resistance improvers such as rubber; antioxidants such as hindered phenols and phosphorus-based antioxidants; nucleating agents such as metal salts and sorbitol acetals; and anti-blocking agents.

[0145] The thermoplastic resin composition of the present disclosure can be obtained, for example, by a production method including a mixing step of mixing the resin (A) and the thermoplastic resin (B) using a twin-screw extruder. This allows the dispersed particle size of the resin (A) to be adjusted to a range preferred for improving processability. The present disclosure also relates to a production method for the above-mentioned thermoplastic resin composition including the mixing step.

[0146] By using a twin-screw extruder, the materials can be mixed (kneaded) while applying shear force, so that the dispersed particle size of the resin (A) can be easily adjusted. In this case, the mixing (kneading) is preferably melt-kneading. When melt-kneading is performed, each component may be melted during the mixing step or before the mixing step.

[0147] The twin-screw extruder preferably comprises a screw having a plurality of screw elements, each of which includes two or more kneading disc elements, attached to its shaft, and a barrel incorporating the two screws, and the kneading area ratio, which is the value obtained by dividing the total length of the kneading disc elements by the total length of the screws, is 0.01 or more. The total lengths of the kneading disc elements and the screws are usually measured in mm.

[0148] The twin-screw extruder includes, for example, two screws, a barrel containing the two screws, a raw material supply port provided in the barrel, and a die provided at the downstream end of the barrel. If necessary, the twin-screw extruder may further include a vacuum vent provided in the barrel.

[0149] The twin-screw extruder may be a co-rotating twin-screw extruder in which two screws inserted into a cylinder of a barrel having an inverted V-shaped through-hole are rotated in the same direction, or a counter-rotating extruder in which two screws are rotated in opposite directions.

[0150] As the twin-screw extruder, a co-rotating twin-screw extruder is preferred because it has excellent conveying capacity, melting / kneading capacity, and separation (dehydration) capacity, is capable of continuous material processing, and is also excellent in terms of improving the efficiency of the resin composition production process.

[0151] The meshing of the two screws may be of a non-intermeshing type, a partial intermeshing type, or a complete intermeshing type.

[0152] The screw used can incorporate a kneading area (described later) at any position on the screw, and therefore has a plurality of screw elements, including two or more kneading disc elements, attached to its shaft.

[0153] Screw elements have the same cross-sectional shape in the direction perpendicular to the axis. Each screw element has a specific function depending on the number of flights, which indicates the number of flights, and the twist angle at which the cross-sectional shape in the direction perpendicular to the axis rotates around the shaft. Screw elements can be classified by function as rotary elements, kneading disk elements, and mixing elements.

[0154] A rotary element is a screw element that has a helix angle that rotates continuously around a shaft and has a conveying capacity.

[0155] The kneading disc element is a screw element composed of a plurality of plate-shaped discs with no twist angle.

[0156] The mixing element is a screw element having a full-flight element with a right-handed thread and a notch formed therein, or a screw element having a full-flight element with a reverse-handed thread and a notch formed therein. The mixing element may or may not have self-cleaning properties.

[0157] The twin-screw extruder preferably has a screw comprising a rotary element, a kneading disc element and a mixing element.

[0158] In the twin-screw extruder, the kneading area ratio is preferably 0.02 or more, more preferably 0.05 or more, even more preferably 0.10 or more, particularly preferably 0.15 or more, and most preferably 0.20 or more. Furthermore, the kneading area ratio is preferably 0.45 or less, more preferably 0.30 or less. When the kneading area ratio is equal to or greater than the lower limit, the resin (A) disperses well in the thermoplastic resin (B), and excellent processability improvement effects are readily achieved. When the kneading area ratio is equal to or less than the upper limit, internal heat generation due to excessive shear heat and deformation compression of the thermoplastic resin A or B by the screw is suppressed, and excessive decomposition of the thermoplastic resin A or B is suppressed.

[0159] When the kneading area ratio is 0.10 or more, the dispersed particle diameter of the resin (A) tends to be 1 to 100 μm, and an excellent effect of improving processability tends to be exhibited. When the kneading area ratio is 0.15 or more, the dispersed particle diameter of the resin (A) tends to be 1 to 50 μm, and an even more excellent effect of improving processability tends to be exhibited.

[0160] When the thermoplastic resin composition of the present disclosure is a masterbatch and the dispersed particle diameter of the resin (A) is 50 μm or less, in order to shorten the melt fracture disappearance time, it is preferable that the "kneading area ratio" x "concentration (mass%) of the resin (A) in the masterbatch" is 1 to 3, or 8 to 12.

[0161] When the thermoplastic resin composition of the present disclosure is a masterbatch and the dispersed particle diameter of the resin (A) is 50 μm or less, in order to reduce the amount of die buildup (DBU) that occurs, it is preferable that the value of "kneading area ratio" x "concentration (mass%) of resin (A) in the masterbatch" is 3.1 to 8.5.

[0162] In the twin-screw extruder, from the viewpoint of efficiently melt-kneading the resin (A) and the thermoplastic resin (B), L / D is more preferably 20 or more, and more preferably 30 to 100. "L / D" is the value obtained by dividing the total screw length L (mm) by the screw diameter D (mm).

[0163] The twin-screw extruder preferably has one or more melting zones in which at least two mixing elements or kneading disk elements among the screw elements are arranged in succession. The twin-screw extruder has a melting zone, which allows the resin (A) and the thermoplastic resin (B), etc. to be melt-kneaded. Because the twin-screw extruder has a melting zone, the residence time of the resin (A) and the thermoplastic resin (B), etc. in the twin-screw extruder is extended by the at least two mixing elements or kneading disk elements arranged in succession. When the resin (A) and the thermoplastic resin (B), etc. pass through the melting zone, shear heat from the screw is imparted to the resin (A) and the thermoplastic resin (B), etc., which causes the resin (A) and the thermoplastic resin (B), etc. to become molten, thereby improving adhesion between the resin (A) and the thermoplastic resin (B), etc. and the screw and suppressing the occurrence of vent-up.

[0164] The number of melting zones is preferably 1 or 2, and more preferably 1. When the number of melting zones is 2 or less, the shear heat or deformation compression action of the resin (A), thermoplastic resin (B), etc. due to the screw is suppressed, and excessive decomposition of the resin (A), thermoplastic resin (B), etc. is suppressed.

[0165] The barrel is made up of multiple barrel blocks connected in series.

[0166] The barrel block is formed with a through hole corresponding to the cross-sectional shape of the screw.

[0167] The vacuum vent is installed for the purpose of removing low-boiling point components contained in the resin (A) and the thermoplastic resin (B), etc., when the resin (A) and the thermoplastic resin (B), etc. are melt-kneaded by the screws of the twin-screw extruder.

[0168] A vacuum vent can be installed in a twin screw extruder, for example, by using a barrel block equipped with a vacuum vent. Vacuum vents may also be installed in multiple barrel blocks.

[0169] When there is only one raw material supply port, the raw material supply port is provided upstream of the most upstream kneading area. When there are multiple raw material supply ports, the first raw material supply port, which is the most upstream of the raw material supply ports, may be provided upstream of the most upstream kneading area, and the other raw material supply ports may be provided downstream of the most upstream kneading area. Resin (A) and thermoplastic resin (B) are preferably supplied from the first raw material supply port. Components other than resin (A) and thermoplastic resin (B) may be supplied from the second raw material supply port or later.

[0170] When the kneaded material is pelletized, the die is preferably one that can extrude the kneaded material to form strands.

[0171] The number of discharge ports in the die may be one or more, but a die having several to several tens of discharge ports is preferred in terms of forming multiple strands and improving productivity.

[0172] When melt-kneading is performed using the twin-screw extruder, first, the resin (A) and the thermoplastic resin (B) are fed into the raw material feed port of the twin-screw extruder. The resin (A) and the thermoplastic resin (B) fed from the raw material feed port of the twin-screw extruder are melt-kneaded in the twin-screw extruder.

[0173] The molten mixture obtained by melt-kneading using the twin-screw extruder is extruded, for example, through a die to form strands. The strands are then cut, for example, by a pelletizer, to obtain pellets of the thermoplastic resin composition.

[0174] The twin-screw extruder may be used for mixing when producing a masterbatch or for other mixing purposes, but is preferably used at least for mixing when producing a masterbatch. The twin-screw extruder may also be used in combination with another mixer; for example, after producing a masterbatch with the twin-screw extruder, the masterbatch and thermoplastic resin may be mixed in another mixer.

[0175] When the twin-screw extruder is used, the extrusion temperature is preferably the melting point of the thermoplastic resin (B) + 10°C or more, more preferably the melting point + 20°C or more, and even more preferably the melting point + 30°C or more, and is preferably the melting point + 160°C or less, more preferably the melting point + 150°C or less, and even more preferably the melting point + 130°C or less.

[0176] In the method for producing a thermoplastic resin composition of the present disclosure, after the mixing step, a discharge step of discharging the mixture or a molding step of molding the discharged mixture using a molding machine or the like may be performed.

[0177] The method for the molding step is not particularly limited, and examples thereof include extrusion molding, injection molding, blow molding, etc., but among these, extrusion molding is preferred in order to effectively exhibit the molding processability.

[0178] An extruder is used for the extrusion molding. Examples of the extruder include a single-screw extruder, a twin-screw extruder, and a tandem extruder. The extruder typically includes a cylinder, a screw housed in the cylinder, a die attached to the tip of the cylinder, and a hopper for supplying pellets to the cylinder.

[0179] The various conditions for the molding are not particularly limited and can be appropriately set depending on the composition and amount of the composition, the shape and size of the desired molded product, and the like.

[0180] <Molded Article> The molded article of the present disclosure uses the thermoplastic resin composition of the present disclosure, and may be obtained, for example, by performing a molding process of molding the thermoplastic resin composition of the present disclosure. The present disclosure also relates to a method for producing the molded article of the present disclosure, which includes a molding process. Note that the thermoplastic resin composition of the present disclosure is suitable for a tubular, film-shaped, or sheet-shaped molded article, but can also be applied to molded articles of other shapes.

[0181] The molding step is the same as that described in the method for producing the processing aid of the present disclosure.

[0182] In the molding step, the molding temperature (extrusion temperature) during molding is generally a temperature equal to or higher than the melting point of the thermoplastic resin (B) and lower than the decomposition temperature of the resin (A). In order to ensure that the effects of the processing aid are significantly exhibited, the temperature is preferably in the range of 160°C or higher and 270°C or lower. In the case of extrusion molding, the molding temperature is sometimes referred to as the extrusion temperature.

[0183] Applications of the molded article of the present disclosure are not particularly limited, but examples include bags, covering materials, tableware such as beverage containers, electric wires, cables, pipes, fibers, bottles, gasoline tanks, and various other industrial molded articles.

[0184] <Method for Evaluating Thermoplastic Resin Composition> The method for evaluating a thermoplastic resin composition according to the present disclosure includes a melting step of heating a thermoplastic resin composition containing a resin (A) and a thermoplastic resin (B) to 180 to 200°C at a heating rate of 5 to 15°C / min and then leaving the composition to melt for 3 to 10 minutes, and an observation step of observing the melted thermoplastic resin composition with a polarizing microscope to evaluate the dispersed particle size of the resin (A).

[0185] According to the evaluation method of the present disclosure, the dispersed particle size of a resin can be evaluated with high accuracy.

[0186] The temperature rise rate is preferably 8 to 14°C / min, more preferably 10 to 12°C / min, and even more preferably 10°C / min. The final temperature during temperature rise is preferably 185 to 195°C, and more preferably 190°C / min. The standing time after temperature rise is preferably 4 to 8 minutes, more preferably 4 to 6 minutes, and even more preferably 5 minutes.

[0187] In the evaluation method of the present disclosure, the thickness of the thermoplastic resin composition to be evaluated is preferably 50 μm or less, more preferably 40 μm or less, and even more preferably 30 μm or less. This allows the thermoplastic resin composition to be heated uniformly. The lower limit of the thickness is not particularly limited, but is usually 5 μm or more.

[0188] Although the embodiments have been described above, it will be understood that various changes in form and details can be made without departing from the spirit and scope of the claims.

[0189] The present disclosure will now be described in more detail with reference to examples, but the present disclosure is not limited to these examples.

[0190] The following materials were used in the examples and comparative examples. (Resin (A)) EVOH: ethylene-vinyl alcohol copolymer (ethylene content: 38 mol%, MFR: 1.6 g / 10 min, melting point: 172°C) PLA: polylactic acid (MFR: 3 g / 10 min, melting point: 153°C) (Thermoplastic resin (B) (carrier resin)) m-LLDPE-2: metallocene catalyst linear low-density polyethylene (MFR: 2.0 g / 10 min, melting point: 121°C, d=0.925, MIR=23.6) ZN-LLDPE-2: Ziegler-Natta catalyst linear low-density polyethylene (MFR: 2.0 g / 10 min, melting point: 121°C, d=0.918, MIR=23.2) (Thermoplastic resin (C) (matrix resin)) m-LLDPE-1: Metallocene catalyst linear low-density polyethylene (MFR: 0.7 g / 10 min, melting point: 123°C, d = 0.926, MIR = 28.1) ZN-LLDPE-1: Ziegler-Natta catalyst linear low-density polyethylene (MFR: 0.8 g / 10 min, melting point: 123°C, d = 0.925, MIR = 27.0)

[0191] Comparative Example 1, Examples 1 to 19 First, a carrier resin (thermoplastic resin (B)) and resin (A) were melt-kneaded in the proportions shown in Tables 1 and 2 using a twin-screw extruder (TEX25αIII manufactured by The Japan Steel Works, Ltd.) under conditions of a cylinder temperature of 180 to 200°C, a die temperature of 200°C, and a screw rotation speed of 300 rpm, to obtain a masterbatch (MB).

[0192] Here, the twin-screw extruder used in the melt-kneading will be described in more detail. FIG. 1 is a schematic diagram showing the twin-screw extruder used in the melt-kneading. The twin-screw extruder 10 includes two screws (not shown), a barrel 12 incorporating the two screws, a raw material supply port 16 provided in the barrel 12, and a strand die head 18 provided at the downstream end of the barrel 12. The barrel 12 includes, in order from the upstream side, a first barrel block C1 to a fifteenth barrel block C15. The raw material supply port 16 is provided in the first barrel block C1. The twin-screw extruder 10 has a melt zone (not shown) extending from a portion of the sixth barrel block C6 to a portion of the thirteenth barrel block C13. All screw elements other than the melt zone are rotary elements. The melt zone is composed of two or more kneading disc elements. The number of kneading disc elements was set so that the kneading area ratio was the value shown in Tables 1 and 2.

[0193] The dispersed particle size of resin (A) in the obtained masterbatch was then evaluated by the dispersion evaluation described below. The results are shown in Tables 1 and 2. The obtained masterbatch was then dry-blended with a matrix resin (thermoplastic resin (C)) in a ratio such that the concentration of resin (A) in the final thermoplastic resin composition would be constant (2000 ppm), and the processability at this time was evaluated by the extrusion evaluation described below. The results are shown in Tables 1 and 2. Note that since the resin (A), thermoplastic resin (C), and thermoplastic resin (B) used all contained no fluorine, the fluorine content in the produced masterbatch and thermoplastic resin composition was 0 mass%.

[0194] <Dispersion Evaluation> (1) Using a microtome, the masterbatch in which the resin (A) is dispersed in the thermoplastic resin (B) is cut perpendicular to the extrusion direction to a thickness of approximately 30 μm, and 10 samples are collected. Each of the collected samples is heated to 190°C at a heating rate of 10°C / min and then left to melt for 10 minutes. (2) The molten thermoplastic resin composition is observed with a polarizing microscope (Nikon ECLIPSE LV100N POL (camera: Nikon DS-Fi2), magnification: 200x). The captured images are analyzed using analysis software (NIS-Elements D) to measure the particle size. One image is taken for each sample, and a total of 10 images are taken, and the average particle size of the dispersed particles in the images is taken as the dispersed particle size. If the particles are not circular, the major axis is taken as the particle size.

[0195] <Extrusion Evaluation> Each material was extruded for 60 minutes using a single-screw extruder (HAAKE Corporation, Rheomex OS, L / D: 33, screw diameter: 20 mm, die diameter: 2 mm) under conditions of a cylinder temperature of 170 to 200°C, a die temperature of 200°C, and a shear rate of 450 / sec, and evaluated for the following items. Prior to each test run, linear low-density polyethylene containing 15% by mass of silica was added to the hopper, the screw rotation speed was increased to 150 rpm, and purging was performed for approximately 15 minutes. Next, the same matrix resin used in the test was added and purging was performed for approximately 15 minutes. After that, the screw rotation speed was returned to 30 rpm and extrusion was continued until the temperature stabilized. After confirming that the initial pressure had returned, the next experiment was conducted. If the initial pressure had not returned, the above purging procedure was repeated until the initial pressure returned, and the next experiment was conducted. (Melt fracture (MF) disappearance time) Using only the matrix resin, extrusion was performed until the pressure stabilized with melt fracture occurring over the entire surface, and the point at which the screw became visible thereafter was set to zero, and extrusion was continued for 60 minutes. In cases where a processing aid or masterbatch was used, these were added to the hopper at zero. The appearance of the strand at the beginning of extrusion and the strand at the end of extrusion was confirmed visually and tactilely. The time from zero as described above until the disappearance of the MF observed at the beginning of extrusion was measured. The shorter the time, the better. Samples in which MF did not disappear were marked with "-". (Die buildup (DBU)) For samples in which MF had completely disappeared, extrusion evaluation was performed in a long-run molding (3 hours), and the state of the die after extrusion was visually confirmed and the presence or absence of DBU (eye discharge) was evaluated. Evaluation was made on a 5-point scale from 1 to 5. The smaller the value, the less DBU was generated and the better, with 1 indicating no DBU.

[0196]

[0197]

[0198] 10: Twin-screw extruder 12: Barrel 16: Raw material supply port 18: Strand die head C1 to C15: 1st barrel block to 15th barrel block

Claims

1. A thermoplastic resin composition comprising a resin (A) and a thermoplastic resin (B), wherein the resin (A) contains a structural unit represented by the following formula 1, and the dispersed particle diameter of the resin (A) is 1 to 100 μm. -X-(CR １ R ２ ) ｎ -Y-(CR ３ R ４ ) ｍ -Z- (Formula 1) (In Formula 1, X is a divalent group which may have a single bond or a functional group, Y and Z are each independently a single bond, -O-, -C(=O)-, -C(=O)O-, -OC(=O)O-, -C(=NR')-, -C(=NR')O-, -OC(=NR')O-, -S-, -S(=O)-, -S(=O)O-, -OS(=O)O-, -S(=O) ２ -, -S(=O) ２ O-, -OS(=O) ２ O-, -P(=O)-, -P(=O)O-, -OP(=O)O-, -P(=O) ２ (-), -P(=O) ２ O-, -OP(=O) ２ O-, -NR'-, and -C(OR')R'- (wherein R' is independently at each occurrence a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms).) A group composed of at least one selected from the group, R １ , R ２ , R ３ and R ４ are each independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, n and m are each independently an integer of 0 to 10, and at least one of X, Y and Z is -C(=O)-, -C(=O)O-, -OC(=O)O- or -C(OR')R'-.) 2. The thermoplastic resin composition according to claim 1, which substantially does not contain fluorine.

3. In the formula 1, X is X １ and X ２ is a divalent group composed of at least one selected from the group consisting of, and X １ is -C(=O)-, -C(=NR')-, -S(=O) ２ -, -NR'-, -CR'R'-, and -C(OR')R'- (wherein R' is, independently at each occurrence, a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms), and X ２ is an aromatic hydrocarbon group having 1 to 12 carbon atoms which may have a substituent. The thermoplastic resin composition according to claim 1 or 2 4. In the formula 1, X is a divalent group containing at least one selected from the group consisting of -C(=O)-, -CR'R'- and -C(OR')R'- (wherein R' is independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms in each occurrence). The thermoplastic resin composition according to claim 3.

5. In the formula 1, Y and Z are each independently a group composed of at least one selected from the group consisting of a single bond, -O-, -C(=O)-, -C(=O)O-, -C(=NR')-, -C(=NR')O-, -S-, -S(=O)2-, -S(=O)2O-, -NR'- and -C(OR')R'- (wherein R' is independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms in each occurrence). The thermoplastic resin composition according to any one of claims 1 to 4.

6. In the formula 1, Y and Z are each independently a group composed of at least one selected from the group consisting of a single bond, -O-, -C(=O)- and -C(=O)O-. The thermoplastic resin composition according to claim 5.

7. The resin (A) is at least one selected from the group consisting of ethylene-vinyl alcohol copolymer and polylactic acid. The thermoplastic resin composition according to any one of claims 1 to 6.

8. The dispersed particle diameter of the resin (A) is 5 to 100 μm. The thermoplastic resin composition according to any one of claims 1 to 7.

9. The thermoplastic resin (B) is a polyolefin resin. The thermoplastic resin composition according to any one of claims 1 to 8.

10. The thermoplastic resin (B) is a metallocene-catalyzed linear low density polyethylene. The thermoplastic resin composition according to any one of claims 1 to 9.

11. The thermoplastic resin composition is a masterbatch, and the content of the resin (A) is 8 to 50% by mass. The thermoplastic resin composition according to any one of claims 1 to 10.

12. The thermoplastic resin composition includes a masterbatch containing the resin (A) and the thermoplastic resin (B), and a thermoplastic resin (C), and the content of the resin (A) is 0.1 to 1.0% by mass. The thermoplastic resin composition according to any one of claims 1 to 10.

13. The thermoplastic resin (C) is a metallocene-catalyzed linear low density polyethylene. The thermoplastic resin composition according to claim 12.

14. A molded article using the thermoplastic resin composition according to any one of claims 1 to 13.

15. The molded article according to claim 14, which is tubular, film-like or sheet-like.

16. A method for producing a thermoplastic resin composition according to any one of claims 1 to 13, comprising a mixing step of mixing the resin (A) and the thermoplastic resin (B) using a twin-screw extruder.

17. The method for producing a thermoplastic resin composition according to claim 16, wherein the twin-screw extruder includes a screw having a plurality of screw elements with two or more kneading disk elements attached to a shaft, and a barrel having two of the screws built therein, and a kneading area ratio, which is a value obtained by dividing the total length of the kneading disk elements by the total length of the screw, is 0.01 or more.

18. An evaluation method for a thermoplastic resin composition, comprising a melting step of heating a thermoplastic resin composition containing a resin (A) and a thermoplastic resin (B) to 180 to 200 °C at a heating rate of 5 to 15 °C / min and then allowing it to stand for 3 to 10 minutes to melt, and an observation step of evaluating the dispersed particle diameter of the resin (A) by observing the melted thermoplastic resin composition with a polarized light microscope.

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