Thermoplastic resin composition, molded body, method for manufacturing thermoplastic resin composition, and method for evaluating thermoplastic resin composition

Abstract

To provide a thermoplastic resin composition having good processibility, a molded body and a method for manufacturing a thermoplastic resin composition.SOLUTION: A thermoplastic resin composition contains a resin (A) and a thermoplastic resin (B), wherein the resin (A) includes a structural unit represented by formula 1: -X-(CR1R2)n-Y-(CR3R4)m-Z-, and a dispersion particle diameter of the resin (A) is 1 to 100 μm.SELECTED DRAWING: None

Description

Technical Field

[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.

Background Art

[0002] In the processing of melt-processable thermoplastic resins, it is necessary to extrude at a high speed in order to improve productivity and reduce costs. However, melt-processable thermoplastic resin compositions always have a critical shear rate, and when this rate is exceeded, a state called melt fracture occurs, where the surface becomes rough and a good molded product cannot be obtained.

[0003] As a method for improving the processability of thermoplastic resins, for example, Patent Document 1 proposes a method containing ethylene vinyl alcohol, and Patent Document 2 proposes a method containing a surfactant and polyethylene glycol. However, the effect was not sufficient.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0005] An object of the present disclosure is to provide a thermoplastic resin composition, a molded article, and a method for producing a thermoplastic resin composition with good processability. Another object of the present disclosure is to provide a method for evaluating a thermoplastic resin composition that can accurately evaluate the dispersed particle diameter of the resin.

Means for Solving the Problems

[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 size 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 represents a single bond or a divalent group which may have a functional group, Y and Z each independently represent a group consisting of at least one selected from the group consisting of 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)2O-, -OS(=O)2O-, -P(=O)-, -P(=O)O-, -OP(=O)O-, -P(=O)2-, -P(=O)2O-, -OP(=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); R 1 , R 2 , R 3 and R 4 each independently represents 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; 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) relates to a compound represented by the formula 1, in which X is 1 and X 2 is a divalent group consisting of at least one selected from the group consisting of X1 is a group composed of at least one selected from the group consisting of -C(=O)-, -C(=NR’)-, -S(=O)2-, -NR’-, -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). X 2 is the thermoplastic resin composition according to the present disclosure (1) or (2), which is an aromatic hydrocarbon group having 1 to 12 carbon atoms and may have a substituent.

[0009] The present disclosure (4) is the thermoplastic resin composition according to the present disclosure (3), wherein 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, 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 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, 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 composed 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 polylactic acid.

[0013] The present disclosure (8) is a 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 a 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 a 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 a 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% by mass.

[0017] The present disclosure (12) is a thermoplastic resin composition according to any one of the present disclosures (1) to (10), wherein 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.

[0018] The present disclosure (13) is a 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 a molded article according to the present disclosure (14), which is tubular, film-like or sheet-like.

[0021] The present disclosure (16) is a method for producing a 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) includes a screw in which a plurality of screw elements each including two or more kneading disk elements are attached to a shaft, and a barrel containing two of the screws. It is a method for producing a thermoplastic resin composition according to the present disclosure (16), wherein the kneading area ratio, which is the value obtained by dividing the total length of the kneading disk elements by the total length of the screw, is 0.01 or more.

[0023] The present disclosure (18) 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 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. It is a method for evaluating a thermoplastic resin composition.

Advantages of the Invention

[0024] According to the present disclosure, it is possible to provide a thermoplastic resin composition with good processability, a molded article, and a method for producing a thermoplastic resin composition. Further, according to the present disclosure, it is possible to provide a method for evaluating a thermoplastic resin composition capable of highly accurately evaluating the dispersed particle diameter of a resin.

Brief Description of the Drawings

[0025]

Figure 1

Embodiments for Carrying Out the Invention

[0026] Hereinafter, the present disclosure will be specifically described.

[0027] <Thermoplastic Resin Composition> The thermoplastic resin composition of the present disclosure includes a resin (A) and a thermoplastic resin (B), 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. -X-(CR 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 group consisting of at least one selected from the group consisting of 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)2O-, -OS(=O)2O-, -P(=O)-, -P(=O)O-, -OP(=O)O-, -P(=O)2-, -P(=O)2O-, -OP(=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); R 1 , R 2 , R 3 and R 4 each independently represents 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; At least one of X, Y, and Z is -C(=O)-, -C(=O)O-, -OC(=O)O-, or -C(OR')R'-.

[0028] According to the thermoplastic resin composition of the present disclosure, good processability can be obtained. In particular, good extrusion processability can be obtained even in long-run molding. The thermoplastic resin composition of the present disclosure was completed by finding that the dispersed particle size of the resin (A) is strongly correlated with processability, and that particularly good processability can be 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 X 1 is a group composed of at least one selected from the group consisting of -C(=O)-, -C(=NR’)-, -S(=O)2-, -NR’-, -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). 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 preferably, in each occurrence, independently 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 still more preferably a hydrogen atom or a hydrocarbon group having 1 carbon atom.

[0032] In the above formula 1, Y and Z are each independently preferably 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, in each occurrence, a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms).

[0033] In the above formula 1, Y and Z are each independently preferably a group composed of at least one 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 4is preferably, independently of each other, 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 still 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, still more preferably an integer of 0 to 4, and particularly preferably an integer of 0 to 2.

[0036] In addition, the resin (A) may contain a structural unit other than the structural unit represented by Formula 1. Examples of the structural unit that may be contained in addition to 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; dicarboxylic acids such as oxalic acid, adipic acid, sebacic acid, azelaic acid, dodecanedioic acid, malonic acid, glutaric acid, cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, naphthalenedicarboxylic acid, bis(p-carboxyphenyl)methane, anthracenedicarboxylic 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; lactones such as caprolactone, valerolactone, propiolactone, undecalactone, and 1,5-oxepan-2-one; and the like.

[0037] In the above 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, still more preferably 10% by mass or more, particularly preferably 20% by mass or more, and is preferably 99.9% by mass or less, more preferably 99% by mass or less, still more preferably 95% by mass or less.

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

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

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

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

[0042] When copolymerizing ethylene and vinyl acetate, other vinyl fatty acid esters (such as vinyl propionate, vinyl pivalate, etc.) can also be used in combination. Further, the ethylene-vinyl alcohol copolymer can also contain 0.0002 to 0.2 mol% of a vinyl silane compound as a copolymerization component. Here, examples of the vinyl silane compound include vinyl trimethoxysilane, vinyl triethoxysilane, vinyl tri(β-methoxy-ethoxy)silane, and γ-methacryloxypropyl methoxysilane. Among them, vinyl trimethoxysilane and vinyl triethoxysilane are preferably used.

[0043] When copolymerizing ethylene and vinyl acetate, monomers other than the above-mentioned vinyl fatty acid esters and vinyl silane compounds, for example, α-olefins such as propylene, isobutylene, α-octene, α-dodecene; unsaturated acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid or their anhydrides, salts, or mono- or dialkyl esters, etc.; nitriles such as acrylonitrile, methacrylonitrile, etc.; amides such as acrylamide, methacrylamide, etc.; olefin sulfonic acids such as ethylene sulfonic acid, allyl sulfonic acid, methallyl sulfonic acid or their salts; alkyl vinyl ethers, vinyl ketone, N-vinyl pyrrolidone, vinyl chloride, vinylidene chloride, etc. can be present in a small amount.

[0044] The melting point of the above resin (A) is preferably 65°C or higher, more preferably 70°C or higher, still more preferably 75°C or higher, and even more preferably 80°C or higher, and is preferably 190°C or lower, more preferably 185°C or lower, still 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 melting heat curve when the temperature is raised at a rate of 10°C / min using a differential scanning calorimetry (DSC) apparatus.

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

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

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

[0048] Among the polyolefin polymers, for example, homopolymers (for example, homopolymers of C2-C10 α-olefins, preferably C2-C6 α-olefins) can be mentioned. Specific examples of the homopolymers include homopolyethylene and polypropylene (hPP). For example, taking homopolyethylene as an example, such polymers can be produced, for example, by free radical polymerization in a high-pressure process, and are typically highly branched ethylene homopolymers, often known as LDPE (low density polyethylene), with a density of less than 0.945 g / cm 3 and often less than 0.935 g / cm 3 and, for example, in the range from 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 specified in this specification, all polymer density values are determined according to ASTM D1505. The sample is molded under ASTM D4703-10a, Procedure C, and left standing for 40 hours under ASTM D618-08 (23 ± 2 °C and relative humidity 50 ± 10%) before testing.

[0049] In another example, ethylene monomers can be polymerized using known gas, slurry, and / or solution phase polymerization, for example, 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 phase or slurry phase polymerization with any of the above catalysts), it is called HDPE (high density polyethylene) and typically has a density in the range of from 0.945 to 0.970 g / cm 3 as, above 0.945 g / cm 3 and having a density of or more.

[0050] Further examples of polymers include copolymers of two or more C2-C40 α-olefins, such as C2-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-C20 α-olefin comonomers (1-butene, 1-hexene, 1-octene, or mixtures of two or more thereof are preferred in various embodiments), such as C4-C12 α-olefin comonomers. Ethylene copolymers (e.g., copolymers of ethylene and one or more C3-C20 α-olefins) can contain at least 90, 94, 95, or 96 wt% (e.g., ranging from low values of 80, 85, 90, 80, 85, 93, 93, 95, 96, or 97 wt% to high values of 94, 95, 95.5, 91, 92, 97, 94, 97.5, or 98 wt%), and can contain at least 96 wt% or 96.5 wt% of ethylene-derived units, based on the total amount of ethylene-derived units and comonomer-derived units, and can include ranges from any of the low values to any of the high values described above. For example, the ethylene copolymer can contain 94 or 95 wt% to 97 or 98 wt% of ethylene-derived units, based on the total amount of ethylene-derived units and comonomer-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-C20 α-olefins such as units derived from butene, hexene, and / or octene) can be present in the ethylene copolymer in amounts ranging from low values of 2, 2.5, 3, 3.5, 4, 4.5, 5, or 6 wt% to high values of 3, 4, 5, 6, 7, 8, 9, 10, 15, or 20 wt%, and the range is from the low value to the intended high value described above (provided the high value is greater than the low value).

[0051] For ethylene-based, propylene-based, or other α-olefin-based copolymers, several suitable comonomers are already known, but in various embodiments, other α-olefin comonomers are contemplated. For example, the α-olefin comonomer may be linear or branched, and two or more comonomers can be used if desired. Examples of suitable comonomers include linear C3-C20 α-olefins (such as butene, hexene, octene as already mentioned), and α-olefins having one or more C1-C3 alkyl branches or aryl groups. For example, 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; styrene. The above list of comonomers is merely exemplary and is not intended to be limiting. In some embodiments, the comonomer includes propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene and styrene.

[0052] In certain embodiments, the polymer can include an ethylene copolymer or, alternatively, can be an ethylene copolymer (in accordance with those described above). The ethylene copolymer can be produced by gas, slurry or solution phase polymerization, and some particularly preferred ethylene copolymers can be produced by gas or slurry phase polymerization. Specific examples are linear low density polyethylene (LLDPE), a copolymer of ethylene and one or more α-olefins, and are 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 LLDPE has a density 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 can have a density within the range of high concentrations. LLDPE can be distinguished from the above-mentioned LDPE in several respects, many of which are well-known in the art, including the degree of branching (which is often minimal, if any) in the produced polymer. It should be noted that LLDPE has substantially fewer long-chain branches. In certain embodiments, the polymer of the polymer composition is or includes metallocene-catalyzed LLDPE (mLLDPE). In still other embodiments, the polymer of the polymer composition is or includes Ziegler-Natta-catalyzed LLDPE (or ZN-LLDPE).

[0053] Also, in some embodiments, the density of the polymer is in the range of 0.905 to 0.945 g / cm 3 For example, from any of the low values of 0.905, 0.907, 0.908, 0.910, 0.911, 0.912, 0.913, 0.914, or 0.915 g / cm 3 to any of the high values 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 and the range is from the above-mentioned low values to high values as intended 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 still other embodiments, the polymer may be a higher density (e.g., HDPE) having a density within the range of 0.945 g / cm 3 to 0.970 g / cm 3 .

[0054] Furthermore, the rheological properties of the polymer can affect the processing aid composition for molding the molded article. Generally, the PPA composition is preferably used in a polymer having a melt index (MI or I2, measured at 190 °C and a load of 2.16 kg 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 according to ASTM D1238 at 190 °C and a load of 21.6 kg) to the melt index, or HLMI / MI) can generally have an MIR in 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 in the polymers of some embodiments. Optionally, the MI in such polymers can be less than 1.5 g / 10 min, such as less than 1.0 g / 10 min (e.g., from 0.1, 0.2, or 0.5 g / 10 min to 1.0; or any of 1.1, 1.2, 1.3, 1.4, or less than 1.5 g / 10 min).

[0055] Also, the above LLDPE is preferably at least one selected from the group consisting of Ziegler-Natta catalyst type LLDPE and metallocene catalyst type LLDPE. Particularly, metallocene catalyst type LLDPE is preferred.

[0056] The above thermoplastic resin (B) may or may not have crystallinity. When the above thermoplastic resin (B) has crystallinity, those having a melting point of 80 to 300 °C are preferred, and those having a melting point of 100 to 200 °C are more preferred. The non-crystalline thermoplastic resin (B) preferably has a processing temperature substantially equivalent to that of the crystalline thermoplastic resin (B) whose melting point range is indicated.

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

[0058] In the thermoplastic resin composition of the present disclosure, the dispersed particle diameter of the resin (A) is 1 to 100 μm. If it is in 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, still more preferably 40 μm or less, and particularly preferably 30 μm or less.

[0059] When the dispersed particle diameter of the resin (A) is 10 μm or more, the melt fracture disappearance time becomes short. Therefore, from the viewpoint of the melt fracture disappearance time, the dispersed particle diameter of the resin (A) is preferably 10 to 100 μm, more preferably 15 to 50 μm, and still 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 build-up (DBU) generated decreases. 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, cut the thermoplastic resin composition in which the resin (A) is dispersed in the thermoplastic resin (B) so that the thickness becomes about 30 μm perpendicular to the extrusion direction, and collect 10 samples. After heating the collected samples to 190 °C at a heating rate of 10 °C / min each, let them stand for 10 minutes to melt. (2) Observe the thermoplastic resin composition after melting under a polarized light microscope (Nikon ECLIPSE LV100N POL (camera: Nikon DS-Fi2), magnification: 200x). Measure the particle size by analyzing the captured images with analysis software (NIS-Elements D). Take 1 image for each sample, for a total of 10 images, and take the average value of the particle sizes of the dispersed particles in the images as the dispersed particle size. When the particles are not circular, take the major axis as the particle size.

[0062] The dispersed particle size of the resin (A) can be adjusted, for example, according to the conditions during mixing. Specifically, if the shear force applied to the object is strong, the dispersed particle size will be small, and if the shear force applied to the object is weak, the dispersed particle size will be large. Examples of methods for adjusting the dispersed particle size of the resin (A) to a range favorable for improving processability include, for example, the method for producing the thermoplastic resin composition of the present disclosure described below.

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

[0064] When the thermoplastic resin composition of the present disclosure is a masterbatch, it is particularly useful as a processing aid for thermoplastic resins (especially 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, still more preferably 1 g / 10 min or more, even more preferably 1.5 g / 10 min or more, and preferably 100 g / 10 min or less, more preferably 50 g / 10 min or less, still more preferably 30 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 range, the effect of improving processability is better.

[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, still 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, still 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, still 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, still more preferably 95% by mass or more, 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, still more preferably 0.1% by mass or more, and is preferably 5% by mass or less, more preferably 3% by mass or less, still more preferably 2% by mass or less, 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). Thereby, good processability can be obtained. In particular, good extrusion processability can be obtained even during long-run molding. Furthermore, the storage stability of the extruded product is also excellent.

[0071] As the above-mentioned thermoplastic resin (C), the same ones as the above-mentioned thermoplastic resin (B) can be used, 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 above-mentioned thermoplastic resin (B) and the above-mentioned thermoplastic resin (C) may be of the same type or different types.

[0072] The thermoplastic resin composition of the present disclosure preferably contains substantially no fluorine. "Substantially free of fluorine" means that the fluorine content in the above processing aid is 10 ppm or less (preferably 1 ppm or less, more preferably 0.1 ppm or less). It is particularly preferred that the processing aid of the present disclosure does not contain fluorine (the fluorine content is 0% by mass).

[0073] The water 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, still 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. Measure the mass of the thermoplastic resin composition of the present disclosure before and after heating at 130 °C for 24 hours, and calculate according to the following formula. Take the sample three times, calculate each time, then find the average, and adopt the average value. Water content (% by mass) = [(mass of the thermoplastic resin composition before heating (g)) - (mass of the thermoplastic resin composition after heating (g))] / (mass of the thermoplastic resin composition before heating (g)) × 100

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

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

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

[0078] The above polyol can be represented by, for example, A[(OR 11 ) x OR 12 y . In the formula, A is usually an alkylene having one or more ether bonds, y is 2 or 3, and (OR 11 ) x is a poly(oxyalkylene) chain having a plurality (x) of oxyalkylene groups OR 11 . Each R 11 is independently C2-C5 alkylene, and in some embodiments, C2-C3 alkylene. 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 bonded to the O of OR 12 . x is 10-230,000.

[0079] The above polyol can be a homopolymer of poly(oxypropylene) in which R 11 is -CH2CH2-, or a homopolymer of poly(oxyethylene) in which R 11 is -C3H6-, etc.

[0080] ​ The above polyol may have a chain of randomly distributed oxyalkylene groups (e.g., -OC2H4- and -OC3H6- units which are copolymers), or an alternating block consisting of repeating oxyalkylene groups (e.g., (-OC2H4-) a1 block and (-OC3H6-) b1 block, where a1 + b1 is between 10 and 230,000).

[0081] In some embodiments of the above polyol, A is ethylene, -CH2-CH(-)-CH2- (derived from glycerol), CH3CH2C(CH2-)3 (derived from 1,1,1-trimethylolpropane), poly(oxypropylene), -CH2CH2-O-CH2CH2- or -CH2CH2-O-CH2CH2-O-CH2CH2-, and R 12 is hydrogen, methyl, butyl, phenyl, benzyl, acetyl, benzoyl or stearyl.

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

[0083] The above polyol 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 above polyethylene glycol is preferably 1,000 or more, more preferably 3,000 or more, still more preferably 5,000 or more, and is preferably 50,000 or less, more preferably 45,000 or less, still more preferably 40,000 or less. Within the above range, the effect of improving processability is better. In this specification, the number average molecular weight is determined by calculation from the hydroxyl value measured in accordance with JIS K0070.

[0085] The viscosity average molecular weight (Mv) of the above polyethylene oxide is preferably 100,000 or more, more preferably 120,000 or more, still more preferably 140,000 or more, and is preferably 10,000,000 or less, more preferably 1,600,000 or less, still more preferably 500,000 or less. Within the above range, 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 with various polymer concentrations c (g / dl) in pure water is measured at 35°C. Based on the relationship between the reduced viscosity (ηsp / c) obtained by dividing the specific viscosity by the polymer concentration c and the polymer concentration c, [η] is calculated by extrapolating the polymer concentration c to 0. [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 above polycaprolactone may be a homopolymer of ε-caprolactone or a modified polycaprolactone. Examples of the above modified polycaprolactone include those modified by coexisting with 1,4-butanediol or the like during the ring-opening polymerization of ε-caprolactone, and those modified with an ether or ester group or the like at the terminal of the polymer.

[0087] The weight average molecular weight (Mw) of the above polycaprolactone is preferably 2,000 or more, more preferably 10,000 or more, still more preferably 25,000 or more, and is preferably 100,000 or less, more preferably 95,000 or less, still more preferably 90,000 or less. Within the above range, the effect of improving processability becomes better. In this specification, the weight average molecular weight is measured by polystyrene conversion using gel permeation chromatography (GPC) method.

[0088] The melting point of the above polycaprolactone is preferably 80 °C or less, more preferably 75 °C or less, still more preferably 70 °C or less, particularly preferably 68 °C or less, and is preferably 10 °C or more, more preferably 20 °C or more, still more preferably 45 °C or more. Within the above range, the effect of improving processability becomes better.

[0089] The above silicone can in principle be all organosilicon compounds known to those skilled in the art by 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 (editors), Volume 5: "Organische Zwischenverbindungen, Polymere" [Organic Intermediates, Polymers], Chapter: "Silicones", Wiley-VCH, Weinheim, 2005.

[0090] Silicone can be a substituted or unsubstituted linear oligo- or polydiorganosiloxane, a branched silicone polymer, a silicone resin or a crosslinked silicone polymer. Naturally, mixtures consisting of various silicone polymers can also be used. As already mentioned, silicone-containing copolymers, for example, polyether-functional silicone, silicone containing urea or urethane units or silicone block copolymers with organic polymers can also be used. For the purpose of better additivity, the use of high molecular weight polydiorganosiloxanes containing non-silicone components, for example, fillers such as particulate silicic acid, chalk, talc and sheet silicates, is particularly preferred.

[0091] Preferably, the silicone polymer corresponds to formula A, [R 13 3SiO 1 / 2 a2 [SiR 13 2O 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, and a2, b2, c2, d2 each represent 0 or an integer, and a2 + b2 + c2 + d2 is an integer from 5 to 15000.

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

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

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

[0095] Residue R 13 Preferably binds to the silicone polymer represented by formula A via a Si-C bond, but can also bind to the silicone polymer via an oxygen atom -O-.

[0096] R 13 Preferably has from 1 to 6 carbon atoms. Ethyl residues, phenyl residues, vinyl residues 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 means <0.1×(a2 + b2 + c2 + d2), particularly c2 + d2 <0.05×(a2 + b2 + c2 + d2).

[0099] Preferably, all residues R 13 means that at least 50%, more preferably at least 70%, particularly preferably at least 80% of them are methyl residues.

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

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

[0102] The degree of polymerization of UHMW polysiloxane 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 air-suspended rotary rheometer in accordance with DIN EN ISO 3219:1994 and DIN 53019, where a plate-plate system (diameter 25 mm) with a measurement 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 -1. The viscosity description represents the arithmetic mean value of three individual measurement values performed independently.

[0104] Due to being inexpensive and effective, among 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, particularly preferably between 15 and 30 kPa·s (preferably measured by the above method) are particularly preferred.

[0105] The above-mentioned UHMW polysiloxane includes commercially available UHMW polysiloxanes such as MULTIBASE® MB50-001 and MULTIBASE® MB50-002 manufactured by Dupont, GENIOPLAST® PELLET S, GENIOPLAST® PELLET P PlUS, GENIOPLAST® PE50S08, GENIOPLAST® PP50S12 manufactured by Asahi Kasei Wacker Silicone, and their mixtures, etc. MB50-002 and GENIOPLAST® PELLET S are preferred.

[0106] Silicone polymers are commercially available in the form of pellets / granules or masterbatches so that they can be immediately used, for example, they can be mixed with thermoplastic plastic granules before these further processes.

[0107] The above-mentioned 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 can also be referred to as a "polyamide / polyether block copolymer". Also, it can be abbreviated as "PEBA copolymer" or "PEBA". In some embodiments of the present disclosure, the PEBA copolymer can be represented by the following general formula.

Chemical formula

[0108] Here, PA is a polyamide block, PE is a polyether block, p represents the length of the PEBA copolymer, and represents 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.

Chemical formula

[0109] Here, EG is a first unspecified end group, B is an unspecified crosslinking group, and EG * is a second unspecified end group, and EG, B, and EG * are determined by the synthesis method used to produce the PEBA copolymer. Here, 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, p represents the length of the PEBA copolymer, and represents 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.

Chemical formula

[0110] Here, 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, p represents the length of the PEBA copolymer, and represents the total number of polyamide and polyether blocks.

[0111] The polyamide block in the above PEBA copolymer is 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 a narrow molecular weight polymer standard with techniques known in the art.

[0113] In an embodiment, the number average molecular weight Mn of the polyamide block 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 block 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 number average molecular weight Mn of the PEBA copolymer is from 10,000 to 500,000 g / mol, including sub - ranges within this range and any numbers within this range. For example, in an embodiment of the present disclosure, the number average molecular weight Mn of the PEBA copolymer is from 10,000 to 400,000 g / mol, or from 10,000 to 300,000 g / mol, 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 number average molecular weight Mn of the PEBA copolymer is at least 10,000 g / mol, at least 20,000 g / mol, at least 25,000 g / mol, more than 25,000 g / mol, at least 30,000 g / mol, more than 30,000 g / mol, at least 35,000 g / mol, more than 35,000 g / mol, at least 50,000 g / mol, or more than 50,000 g / mol.

[0115] In an embodiment, the weight average molecular weight Mw of the PEBA copolymer is from 25,000 to 500,000 g / mol, including sub-ranges within this range and any number within this range. For example, in embodiments of the present disclosure, the weight average molecular weight Mw 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 above PEBA copolymer may be randomly distributed.

[0116] The above PEBA copolymer includes a polyamide block and a polyether block, and the polyamide block may account for at least 50% by mass of the copolymer. The above PEBA copolymer includes a polyamide block and a polyether block, and the polyether block may account for at least 50% by mass of the copolymer. Further, the PEBA copolymer includes a polyamide block and a polyether block, and the molar ratio of the polyamide block to the polyether block may be in the range of 1:3 to 3:1, or 1:2 to 2:1, or 3:2 to 1:3, or 2:3 to 3:1, or about 1:1.

[0117] By reacting the above polyamide and polyether block precursors, a PEBA copolymer having a polyamide block and a polyether block can be prepared. For example, lactam, polyether diol, and a chain-limiting diacid are reacted together in the presence of a small amount of water to obtain a PEBA copolymer having polyamide blocks and polyether blocks with variable lengths and a statistically random distribution within the block copolymer chains. The above polyether block is derived from poly(oxyethylene), poly(oxypropylene), or poly(tetramethylene ether) glycol, each of which may be co-condensed with a polyamide block containing carboxylic acid chain ends in its natural state. A chain limiter is also present during the polycondensation reaction to give a PEBA copolymer containing polyamide blocks and polyether blocks randomly distributed within the block copolymer. The above polyether block is 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 is also present during the polycondensation reaction to give a PEBA copolymer containing polyamide blocks and polyether blocks randomly distributed within the block copolymer. The above polyether block can be derived from poly(oxyethylene), also known as polyethylene glycol (PEG). The above polyether block can be derived from poly(oxypropylene), also known as polypropylene glycol (PPG). The above polyether block can be derived from poly(tetramethylene ether) glycol (PTMG), also known as polytetramethylene oxide (PTMEO) or polytetrahydrofuran (PTHF).

[0118] The above 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 selected from polyethylene glycol (PEG), polypropylene glycol (PPG), polytetrahydrofuran (PTHF), or a mixture thereof.

[0119] The above-mentioned 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 which is polyethylene glycol (PEG). In one embodiment of the present disclosure, the PEBA copolymer comprises: i) a polyamide block which is polyamide-12 (PA-12); and ii) a polyether block which is polyethylene glycol (PEG).

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

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

[0122] The above-mentioned PEBA copolymer comprises: i) a polyamide block which is polyamide-12 (PA-12); and ii) a polyether block which is polyethylene glycol (PEG), wherein the polyamide-12 block accounts for about 30% to 70% by mass of the copolymer, and the polyethylene glycol block accounts for about 70% to 30% by mass of the copolymer.

[0123] The above-mentioned PEBA copolymer comprises: i) a polyamide block which is polyamide-12 (PA-12); and ii) a polyether block which is polyethylene glycol (PEG), wherein the polyamide-12 block accounts for about 40% to 60% by mass of the copolymer, and the polyethylene glycol block accounts for about 60% to 40% by mass of the copolymer.

[0124] The above-mentioned PEBA copolymer comprises: i) a polyamide block which is polyamide-12 (PA-12); and ii) a polyether block which is polyethylene glycol (PEG), wherein the polyamide-12 block represents about 45% by mass of the copolymer, and the polyethylene glycol block represents about 55% by mass of the copolymer.

[0125] The above-mentioned PEBA copolymer contains: i) 10 to 20 polyamide blocks which are polyamide-12 (PA-12), and ii) 10 to 20 polyether blocks which are polyethylene glycol (PEG).

[0126] The above-mentioned PEBA copolymer contains: i) a polyamide block which is polyamide-12 (PA-12), and ii) a polyether block which is polyethylene glycol (PEG), and the number-average molecular weight Mn is from about 25,000 to about 75,000 g / mol.

[0127] The above-mentioned PEBA copolymer contains: i) a polyamide block which is polyamide-12 (PA-12), and ii) a polyether block which is polyethylene glycol (PEG), and the number-average molecular weight Mn is from about 50,000 to about 75,000 g / mol. The above-mentioned PEBA copolymer contains: i) a polyamide block which is polyamide-12 (PA-12) and ii) a polyether block which is polyethylene glycol (PEG), and the number-average molecular weight Mn is about 66,100 g / mol.

[0128] The above-mentioned PEBA copolymer contains: i) a polyamide block which is polyamide-12 (PA-12), and ii) a polyether block which is polyethylene glycol (PEG), and the weight-average molecular weight Mw is from about 100,000 to about 150,000 g / mol.

[0129] The above-mentioned PEBA copolymer contains: i) a polyamide block which is polyamide-12 (PA-12), and ii) a polyether block which is polyethylene glycol (PEG), and the weight-average molecular weight Mw is from about 125,000 to about 150,000 g / mol.

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

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

[0132] The PEBA copolymer includes 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 from about 50% to 35% by mass of the copolymer, and the polyethylene glycol block represents from about 50% to 65% by mass of the copolymer.

[0133] The PEBA copolymer includes 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 includes 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 includes i) a polyamide block that is polyamide-12 (PA-12), and ii) a polyether block that is polytetrahydrofuran (PTHF).

[0135] The above-mentioned PEBA copolymer contains i) a polyamide block which is polyamide-12 (PA-12), and ii) a polyether block which is polytetrahydrofuran (PTHF), where the polyamide-12 block represents from about 75% to 10% by mass of the copolymer, and the polytetrahydrofuran block represents from about 25% to 90% by mass of the copolymer.

[0136] The above-mentioned PEBA copolymer contains i) a polyamide block which is polyamide-12 (PA-12), and ii) a polyether block which is polytetrahydrofuran (PTHF), where the polyamide-12 block represents from about 80% to 60% by mass of the copolymer, and the polytetrahydrofuran block represents from about 20% to 40% by mass of the copolymer.

[0137] The above-mentioned PEBA copolymer contains i) a polyamide block which is polyamide-12 (PA-12), and ii) a polyether block which is polytetrahydrofuran (PTHF), where the polyamide-12 block represents from about 40% to 60% by mass of the copolymer, and the polytetrahydrofuran block represents from about 60% to 40% by mass of the copolymer.

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

[0139] The above-mentioned PEBA copolymer includes i) a polyamide block which is polyamide-12 (PA-12), and ii) a polyether block which is polytetrahydrofuran (PTHF), and has a number average molecular weight Mn of about 25,000 to about 75,000 g / mol. The above-mentioned PEBA copolymer includes i) a polyamide block which is polyamide-12 (PA-12), and ii) a polyether block which 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 includes i) a polyamide block which is polyamide-12 (PA-12), and ii) a polyether block which is polytetrahydrofuran (PTHF), and has a number average molecular weight Mn of about 50,000 g / mol.

[0140] The above-mentioned PEBA copolymer includes i) a polyamide block which is polyamide-6 (PA-6), and ii) a polyether block which is polytetrahydrofuran (PTHF). The above-mentioned PEBA copolymer includes i) a polyamide block which is polyamide-11 (PA-11), and ii) a polyether block which is polytetrahydrofuran (PTHF). The above-mentioned PEBA copolymer is a commercially available elastomer and is sold under the trade name of PEBAX (registered trademark).

[0141] The above-mentioned 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® 30R51 SA 01, PEBAX RNEW 35R53 SP01, 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 above-mentioned PEBA copolymer is a commercially available elastomer and is sold under the trade names VESTAMID® or VESTAMID E.

[0142] The above-mentioned 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. Among them, Pebax MV1072 is preferred.

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

[0144] Other components include, for example, anti-sticking agents; ultraviolet absorbers; flame retardants; reinforcing materials such as glass fibers and glass powders; stabilizers such as minerals and flakes; lubricants such as silicone oil and molybdenum disulfide; pigments such as titanium dioxide and valve handles; conductive agents such as carbon black; impact resistance improvers such as rubber; antioxidants such as hindered phenols and phosphorus-based compounds; nucleating agents such as metal salts and acetals of sorbitol, and anti-blocking agents can also be used.

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

[0146] By using a twin-screw extruder, it is possible to mix (knead) the material while applying a shearing force, so that the dispersed particle diameter of the above resin (A) can be easily adjusted. In this case, the mixing (kneading) is preferably melt kneading. When performing melt kneading, each component may be melted in the mixing step, or may be melted before the mixing step.

[0147] The above twin-screw extruder includes a screw in which a plurality of screw elements including two or more kneading disk elements are attached to a shaft, and a barrel containing two of the above screws, and the kneading area ratio, which is the value obtained by dividing the total length of the kneading disk elements by the total length of the screw, is preferably 0.01 or more. The unit of the total length of the kneading disk element and the screw is usually mm.

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

[0149] The above twin-screw extruder may be a co-rotating twin-screw extruder that rotates two screws in the same direction through the cylinder of a barrel in which an inverted V-shaped through-hole is formed, or may be a counter-rotating extruder that rotates two screws in opposite directions.

[0150] As the above twin-screw extruder, a co-rotating twin-screw extruder is preferable because it is excellent in conveying ability, melting and kneading ability, separation (dehydration) ability, can continuously process materials, and is also excellent in improving the efficiency of the manufacturing process of the resin composition.

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

[0152] As the screw, one that can incorporate the kneading area described later at any position of the screw is used. Therefore, as the screw, one having a plurality of screw elements including two or more kneading disk elements mounted on the shaft is used.

[0153] The screw elements have the same cross-sectional shape in a direction perpendicular to the axis. In the screw elements, unique functions are generated according to the number of threads, which means 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. Examples of the screw elements include rotary elements, kneading disk elements, and mixing elements according to their functions.

[0154] The rotary element is a screw element that has a continuous twist angle around the shaft and has a conveying ability.

[0155] The kneading disk element is a screw element composed of a plurality of plate-like disks without a twist angle.

[0156] The mixing element is a screw element formed by forming a notch in a full-flight element with a right-handed thread or a screw element formed by forming a notch in a full-flight element with a left-handed thread. The mixing element may or may not have self-cleaning properties.

[0157] As the screw of the twin-screw extruder, one composed of a rotary element, a kneading disk element, and a mixing element is preferably used.

[0158] In the above twin-screw extruder, the kneading area ratio is preferably 0.02 or more, more preferably 0.05 or more, still more preferably 0.10 or more, particularly preferably 0.15 or more, and most preferably 0.20 or more. Also, the kneading area ratio is preferably 0.45 or less, more preferably 0.30 or less. If the kneading area ratio is at least the above lower limit value, the resin (A) is well dispersed in the thermoplastic resin (B), and it is easy to exhibit an excellent processability improvement effect. If the kneading area ratio is at most the above upper limit value, excessive shear heating by the screw on the thermoplastic resin A or B and internal heating due to deformation compression are 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 tends to exhibit an excellent processability improvement effect. 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 tends to exhibit a further excellent processability improvement effect.

[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 "kneading area ratio" × "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 generation amount of die build-up (DBU), it is preferable that "kneading area ratio" × "concentration (mass%) of the resin (A) in the masterbatch" is 3.1 to 8.5.

[0162] In the above 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 a value obtained by dividing the total screw length L (mm) by the screw diameter D (mm).

[0163] It is preferable that the twin-screw extruder has one or more melting zones in which at least one of the mixing elements and the kneading disk elements among the screw elements are arranged continuously in two or more. By having a melting zone in the twin-screw extruder, resins (A) and thermoplastic resins (B) are melt-kneaded. Since the twin-screw extruder has a melting zone, the residence time of resins (A) and thermoplastic resins (B) in the twin-screw extruder becomes longer due to at least one of the mixing elements and the kneading disk elements arranged continuously in two or more. And when resins (A) and thermoplastic resins (B) pass through the melting zone, the shearing heat by the screw is applied to resins (A) and thermoplastic resins (B), and resins (A) and thermoplastic resins (B) are in a melted state. Therefore, the adhesion between resins (A) and thermoplastic resins (B) and the screw is improved, and the occurrence of vent-up is suppressed.

[0164] The number of melting zones is preferably one or two, and more preferably one. If the number of melting zones is two or less, the shearing heat generation or deformation compression action by the screw on resins (A) and thermoplastic resins (B) is suppressed, and the decomposition of resins (A) and thermoplastic resins (B) more than necessary is suppressed.

[0165] The barrel is formed by connecting a plurality of barrel blocks in series.

[0166] A through-hole corresponding to the cross-sectional shape of the screw is formed in the barrel block.

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

[0168] The vacuum vent can be installed in a twin-screw extruder, for example, by using a barrel block with a vacuum vent. The vacuum vent may be provided in a plurality of 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 a plurality of raw material supply ports, the first raw material supply port, which is the most upstream one among the raw material supply ports, is 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 after the second raw material supply port.

[0170] When pelletizing the kneaded product, as the die, one that can extrude the kneaded product to form a strand is preferable.

[0171] The number of discharge ports in the die may be one or a plurality. As the die, one having several to several tens of discharge ports is preferable in terms of forming a plurality of strands and having good productivity.

[0172] When performing melt-kneading with the above twin-screw extruder, first, resin (A) and thermoplastic resin (B) are introduced into the raw material supply port of the twin-screw extruder. Resin (A) and thermoplastic resin (B) introduced from the raw material supply port of the twin-screw extruder are melt-kneaded in the twin-screw extruder.

[0173] The molten kneaded product obtained by melt-kneading with a twin-screw extruder is extruded from the die to form a strand, for example. The strand is cut by a pelletizer, for example. Thereby, pellets of the thermoplastic resin composition are obtained.

[0174] The above twin-screw extruder may be used in the mixing during the production of the masterbatch, or may be used in other mixing processes, but it is preferably used at least in the mixing during the production of the masterbatch. Further, the above twin-screw extruder and other mixers may be used in combination. For example, after producing the masterbatch with the above twin-screw extruder, the masterbatch and the thermoplastic resin may be mixed with another mixer.

[0175] When using the above twin-screw extruder, the extrusion temperature is preferably at least the melting point of the thermoplastic resin (B) + 10°C, more preferably the melting point + 20°C or more, still more preferably the melting point + 30°C or more. Also, it is preferably at most the melting point + 160°C, more preferably the melting point + 150°C or less, and still more preferably the melting point + 130°C or less.

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

[0177] The method of the above molding step is not particularly limited, and examples include extrusion molding, injection molding, blow molding, etc. Among them, extrusion molding is preferable in order to effectively exhibit the above moldability.

[0178] For the above extrusion molding, an extruder is used. Examples of the extruder include a single-screw extruder, a twin-screw extruder, a tandem extruder, etc. The extruder generally 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 related to the above molding are not particularly limited and can be appropriately set according to the composition and amount of the composition, the shape and size of the desired molded product, etc.

[0180] <Molded article> The molded article of the present disclosure is obtained by using the thermoplastic resin composition of the present disclosure, and may be obtained, for example, by performing a molding step of molding the thermoplastic resin composition of the present disclosure. The present disclosure is also a method for manufacturing a molded article of the present disclosure including a molding step. The thermoplastic resin composition of the present disclosure is suitable for a molded article in the form of a tube, film or sheet, but can also be applied to molded articles of other shapes.

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

[0182] In the above molding step, the molding temperature (extrusion temperature) during molding is generally carried out at a temperature equal to or higher than the melting point of the above thermoplastic resin (B) and lower than the decomposition temperature of the above resin (A). In terms of the effect of the above processing aid being significantly exerted, it is preferably in the range of 160 °C or higher and 270 °C or lower. In the case of extrusion molding, the above molding temperature may be referred to as the extrusion temperature.

[0183] The use of the molded article of the present disclosure is not particularly limited, and examples include tableware such as bags, coating materials, beverage containers, wires, cables, pipes, fibers, bottles, gasoline tanks, and other various industrial molded articles.

[0184] <Evaluation method of thermoplastic resin composition> The evaluation method of the thermoplastic resin composition of the present disclosure includes a melting step of heating a thermoplastic resin composition containing resin (A) and a thermoplastic resin (B) to 180 - 200 °C at a heating rate of 5 - 15 °C / min and then allowing it to stand for 3 - 10 minutes to melt, and an observation step of observing the dispersed particle diameter of the resin (A) by observing the melted thermoplastic resin composition with a polarized light microscope.

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

[0186] The above heating rate is preferably 8 - 14 °C / min, more preferably 10 - 12 °C / min, and still more preferably 10 °C / min. The final temperature during heating is preferably 185 °C - 195 °C, more preferably 190 °C / min. The standing time after temperature rise is preferably 4 to 8 minutes, more preferably 4 to 6 minutes, and still 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 still more preferably 30 μm or less. Thereby, the thermoplastic resin composition can be heated uniformly. The lower limit of the thickness is not particularly limited, but is usually 5 μm or more.

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

Examples

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

[0190] In the examples and comparative examples, the following materials were used. (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-catalyzed 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-catalyzed 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-catalyzed 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 type 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, the carrier resin (thermoplastic resin (B)) and the resin (A) were melt-kneaded at the ratios shown in Tables 1 and 2 using a twin-screw extruder (TEX25αIII manufactured by Japan Steel Works, Ltd.) under the 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 configuration diagram showing the twin-screw extruder used in the melt-kneading. The twin-screw extruder 10 includes two screws (not shown), a barrel 12 containing 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 sequentially includes the first barrel block C1 to the fifteenth barrel block C15 from the upstream side. The raw material supply port 16 is provided in the first barrel block C1. The twin-screw extruder 10 has a melting zone (not shown) from a part of the sixth barrel block C6 to a part of the thirteenth barrel block C13. All screw elements other than the melting zone are rotary elements. The melting zone is composed of two or more kneading disk elements. The number of kneading disk elements was set so that the kneading area ratio would be the values shown in Tables 1 and 2.

[0193] Next, the dispersed particle diameter of the resin (A) in the obtained masterbatch was evaluated by the following dispersion evaluation. The results are shown in Tables 1 and 2. Next, the obtained masterbatch was dry blended with the matrix resin (thermoplastic resin (C)) at a ratio such that the concentration of resin (A) in the finally obtained thermoplastic resin composition was constant (2000 ppm), and the processability at that time was evaluated by the following extrusion evaluation. The results are shown in Tables 1 and 2. In addition, since none of the resin (A), thermoplastic resin (C), and thermoplastic resin (B) used contained fluorine, the fluorine content in the produced masterbatch and thermoplastic resin composition was 0% by mass.

[0194] <Dispersion evaluation> (1) Using a microtome, cut the masterbatch in which the resin (A) is dispersed in the thermoplastic resin (B) so that the thickness is about 30 μm perpendicular to the extrusion direction, and collect 10 samples. After heating each of the collected samples to 190 °C at a heating rate of 10 °C / min, leave it standing for 10 minutes to melt. (2) Observe the molten thermoplastic resin composition with a polarized light microscope (Nikon ECLIPSE LV100N POL (camera: Nikon DS-Fi2), magnification: 200 times). Measure the particle diameter by analyzing the photographed image with analysis software (NIS-Elements D). Take 1 image for each sample, for a total of 10 images, and take the average value of the particle diameters of the dispersed particles in the image as the dispersed particle diameter. When the particles are not circular, take the major axis as the particle diameter.

[0195] <Extrusion evaluation> Each material was extruded for 60 minutes under the conditions of a cylinder temperature of 170 to 200 °C, a die temperature of 200 °C, and a shear rate of 450 / second using a single-screw extruder (manufactured by HAAKE, Rheomex OS, L / D: 33, screw diameter: 20 mm, die diameter: 2 mm), and evaluated by the following items. Before each test run, linear low-density polyethylene containing 15% by mass of silica was charged into the hopper, the screw rotation speed was increased to 150 rpm, and purging was performed for about 15 minutes. Next, the same matrix resin as that used in the test was charged and purged for about 15 minutes. Then, the screw rotation speed was returned to 30 rpm, and extrusion was performed 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 operation was repeated until the initial pressure returned, and then the next experiment was conducted. (Melt Fracture (MF) disappearance time) Extrusion was performed using only the matrix resin until the pressure stabilized with melt fracture occurring over the entire surface. Then, when the screw became visible after that, that time was set to zero, and extrusion was performed for 60 minutes. For examples using processing aids or masterbatches, these were charged into the hopper at the zero time point. Then, the appearance of the strand at the initial stage of extrusion and the strand at the completion of extrusion was confirmed by visual inspection and palpation. And the time from the zero time point described above until the MF observed at the initial stage of extrusion disappeared was measured. The shorter the time, the better. Those in which MF did not disappear were denoted as "-". (Die Build-up (DBU)) For samples in which MF had completely disappeared, extrusion evaluation was performed in long-run molding (3 hours), the state of the die after extrusion was visually confirmed, and the presence or absence of DBU (die deposit) was evaluated. Evaluation was performed on a 5-point scale from 1 to 5. The smaller the value, the less the amount of DBU generated and the better. 1 indicates that no DBU occurred.

[0196] [Table 1]

[0197] [Table 2] [Explanation of Signs]

[0198] 10: Twin-screw extruder 12: Barrel 16: Raw material supply port 18: Strand die head C1~C15: First barrel block ~ Fifteenth 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 single bond or a divalent group which may have 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, in each occurrence, independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms), and is a group composed of at least one selected from the group consisting of 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 from 0 to 10, 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 a divalent group composed of at least one selected from the group consisting of X １ and X ２ and is a divalent group composed of at least one selected from the group consisting of X １ is a group composed of at least one selected from the group consisting of -C(=O)-, -C(=NR')-, -S(=O) ２ -, -NR'-, -CR'R'-, and -C(OR')R'- (wherein R' is, in each occurrence, independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms). X ２ The thermoplastic resin composition according to claim 1 or 2, wherein X is an aromatic hydrocarbon group having 1 to 12 carbon atoms which may have a substituent.

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 claim 1 or 2.

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)—, —C(═O)O—. The thermoplastic resin composition according to claim 5.

7. The thermoplastic resin composition according to claim 1 or 2, wherein the resin (A) is at least one selected from the group consisting of an ethylene-vinyl alcohol copolymer and polylactic acid.

8. The thermoplastic resin composition according to claim 1 or 2, wherein the dispersed particle diameter of the resin (A) is 5 to 100 μm.

9. The thermoplastic resin composition according to claim 1 or 2, wherein the thermoplastic resin (B) is a polyolefin resin.

10. The thermoplastic resin composition according to claim 1 or 2, wherein the thermoplastic resin (B) is a metallocene-catalyzed linear low-density polyethylene.

11. The thermoplastic resin composition is a masterbatch, The thermoplastic resin composition according to claim 1 or 2, wherein the content of the resin (A) is 8 to 50% by mass.

12. The thermoplastic resin composition includes a masterbatch containing the resin (A) and the thermoplastic resin (B), and a thermoplastic resin (C), The thermoplastic resin composition according to claim 1 or 2, wherein the content of the resin (A) is 0.1 to 1.0% by mass.

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

14. A molded article using the thermoplastic resin composition according to claim 1 or 2.

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 claim 1 or 2, including a mixing step of mixing the resin (A) and the thermoplastic resin (B) using a twin-screw extruder.

17. The twin-screw extruder includes a screw having a plurality of screw elements with two or more kneading disk elements mounted on a shaft, and a barrel having two of the screws built therein, The method for producing a thermoplastic resin composition according to claim 16, wherein the kneading area ratio, which is the 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. A melting step of heating a thermoplastic resin composition containing the resin (A) and the 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 it; An evaluation method for a thermoplastic resin composition including 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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