Thermoplastic resin composition, molded article, method for manufacturing a thermoplastic resin composition, and method for evaluating a 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 body, 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, in order to improve productivity and reduce costs, it is necessary to extrude at a high speed. 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, in Patent Document 1, a method including ethylene vinyl alcohol has been proposed, and in Patent Document 2, a method including a surfactant and polyethylene glycol has been proposed. However, the effects have not been sufficient.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

Means for Solving the Problems

[0006] The present disclosure (1) is a thermoplastic resin composition containing 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 , ,

[0007] , 2 ,

[0008] , , , 1 , R 2 ) n -Y-(CR 3 R 4 ) m -Z- (Formula 1) (In Formula 1, X is a divalent group which may have a single bond or a functional group, Y and Z are each independently a group composed 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 are each independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, n and m are each independently an integer of 0 to 10, [[ID=​​​​​​​​​​​​​​​1 This 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 a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms in each occurrence). X 2 The thermoplastic resin composition according to disclosure (1) or (2) is an aromatic hydrocarbon group having 1 to 12 carbon atoms, which may have substituents.

[0009] The present disclosure (4) is a thermoplastic resin composition according to the present disclosure (3), wherein in formula 1, X is a divalent group comprising 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).

[0010] Disclosure (5) is a thermoplastic resin composition according to any one of Disclosures (1) to (4), wherein in Formula 1, Y and Z are each independently composed of at least one group 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).

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

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

[0013] Disclosure (8) is a thermoplastic resin composition according to any one of Disclosures (1) to (7), wherein the dispersed particle size of the resin (A) is 5 to 100 μm.

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

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

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

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

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

[0019] Disclosure (14) is a molded article using a thermoplastic resin composition described in any of Disclosures (1) to (13).

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

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

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

[0023] The present disclosure (18) includes a melting step in which a thermoplastic resin composition comprising resin (A) and thermoplastic resin (B) is heated to 180 to 200°C at a heating rate of 5 to 15°C / min, and then left to stand for 3 to 10 minutes to melt, The method for evaluating a thermoplastic resin composition includes an observation step of evaluating the dispersion particle size of the resin (A) by observing the thermoplastic resin composition after melting with a polarizing microscope. [Effects of the Invention]

[0024] This disclosure provides a thermoplastic resin composition, a molded article, and a method for producing a thermoplastic resin composition with good processability. Furthermore, this disclosure provides a method for evaluating a thermoplastic resin composition that can accurately evaluate the dispersion particle size of the resin. [Brief explanation of the drawing]

[0025] [Figure 1] This is a schematic diagram showing the twin-screw extruder used in the melt-kneading process in the example. [Modes for carrying out the invention]

[0026] The following provides a detailed explanation of this disclosure.

[0027] <Thermoplastic resin composition> The thermoplastic resin composition of this disclosure comprises resin (A) and thermoplastic resin (B), wherein resin (A) comprises structural units represented by the following formula 1, and the dispersed particle size of resin (A) is 1 to 100 μm. -X-(CR 1 R 2 ) n -Y-(CR 3 R 4 ) m -Z- (Formula 1) (In formula 1, X is a divalent group which may have a single bond or a functional group, Y and Z are each independently composed of at least one group 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 of these is independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms. n and m are independent integers between 0 and 10. At least one of X, Y, and Z is -C(=O)-, -C(=O)O-, -OC(=O)O-, or -C(OR')R'-.

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

[0029] In equation 1 above, X is X 1 and X 2 A divalent group consisting of at least one selected from the group comprising, X 1 This 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 a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms in each occurrence). X 2 It is preferably an aromatic hydrocarbon group having 1 to 12 carbon atoms, which may have substituents.

[0030] In Formula 1 above, X is more preferably a divalent group comprising 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).

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

[0032] In Formula 1 above, it is preferable that Y and Z are each independently composed of at least one group 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).

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

[0034] In formula 1 above, R 1 , R 2 , R 3 and R 4Each of these is preferably a hydrogen atom or a hydrocarbon group having 1 to 7 carbon atoms, more preferably a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, and even more preferably a hydrogen atom or a hydrocarbon group having 1 carbon atom.

[0035] n and m are each preferably integers between 0 and 8, more preferably between 0 and 6, even more preferably between 0 and 4, and particularly preferably between 0 and 2.

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

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

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

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

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

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

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

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

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

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

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

[0047] Examples of the 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, and polyvinyl chloride (PVC). These may be used individually or in combination of two or more. Polyolefin polymers (polyolefin resins) are preferred because they provide a better improvement in processability.

[0048] Among polyolefin polymers, examples include homopolymers (e.g., C2-C10α-olefin homopolymers, preferably C2-C6α-olefin homopolymers). Specific examples of 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 0.945 g / cm³. 3 Less than 0.935 g / cm³ 3 For example, 0.900, 0.905, or 0.910 g / cm³. 3 From 0.920, 0.925, 0.927, 0.930, 0.935, or 0.945 g / cm³ 3 It is within the range. Unless otherwise stated herein, all polymer density values ​​are determined according to ASTM D1505. Samples are molded under ASTM D4703-10a, procedure C, and allowed to stand for 40 hours under ASTM D618-08 (23±2°C and 50±10% relative humidity) 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 polymerization techniques and will not be discussed further herein. When a more linear ethylene homopolymer is produced (e.g., using gas-phase or slurry-phase polymerization with any of the catalysts mentioned above), it is called HDPE (high-density polyethylene) and typically has a density of 0.945 to 0.970 g / cm³. 3 Within the range of 0.945 g / cm³, 3 It has the above density.

[0050] Further examples of polymers include copolymers of two or more C2-C40α-olefins, such as C2-C20α-olefins, such as ethylene-α-olefin copolymers, or propylene-α-olefin copolymers (e.g., propylene-ethylene copolymers or propylene-ethylene-diene ternpolymers (sometimes known as EPDM or PEDM)). Specific examples intended herein include copolymers of ethylene and one or more C3-C20α-olefin comonomers such as C4-C12α-olefin comonomers (1-butene, 1-hexene, 1-octene, or mixtures of two or more thereof are preferred in various embodiments). Ethylene copolymers (for example, copolymers of ethylene and one or more C3-C20α-olefins) can contain at least 90, 94, 95, or 96 wt% (for example, ranging from a low value of 80, 85, 90, 80, 85, 93, 93, 95, 96, or 97 wt% to a high value 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. For example, ethylene copolymers 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. The copolymer may contain 94 or 95% to 97 or 98% by mass of ethylene-derived units. The copolymer balance (based on ethylene-derived units and comonomer-derived units) consists of comonomer-derived units. For example, comonomer units (e.g., units derived from C2-C20α-olefins, such as units derived from butene, hexene, and / or octene) can be present in the ethylene copolymer in values ​​ranging from as low as 2, 2.5, 3, 3.5, 4, 4.5, 5, or 6% by mass to as high as 3, 4, 5, 6, 7, 8, 9, 10, 15, or 20% by mass, with the range being from the lower values ​​to the intended higher values ​​(provided the higher values ​​are greater than the lower values).

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

[0052] In certain embodiments, the polymer may include or (as described above) be an ethylene copolymer. Ethylene copolymers 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 include linear low-density polyethylene (LLDPE), copolymers of ethylene with one or more α-olefins, which are polymerized in the presence of one or more single-site catalysts, e.g., one or more Ziegler-Natta catalysts, one or more metallocene catalysts, and combinations thereof. Such LLDPEs are polymerized at concentrations of 0.900, 0.905, 0.907, and 0.910 g / cm³. 3From low concentrations to 0.920, 0.925, 0.930, 0.935, 0.940, or 0.945 g / cm³ 3 It can have a density within a high concentration range. LLDPE can be distinguished from the LDPE described above in several respects, many of which are well known in the art, including the degree of branching in the manufactured polymer (often negligible, if any), and it should be noted that LLDPE has substantially fewer long-chain branchings. In certain embodiments, the polymer of the polymer composition is or comprises metallocene-catalyzed LLDPE (mLLDPE). In yet other embodiments, the polymer of the polymer composition is or comprises Ziegler-Natta-catalyzed LLDPE (or Zn-LLDPE).

[0053] Furthermore, the polymer density ranges from 0.905 to 0.945 g / cm³ in some embodiments. 3 Within the range of 0.905, 0.907, 0.908, 0.910, 0.911, 0.912, 0.913, 0.914, or 0.915 g / cm³ 3 From any of the following lower values: 0.916, 0.917, 0.918, 0.919, 0.920, 0.924, 0.926, 0.930, 0.935, 0.940, or 0.945 g / cm³ 3 It is within the range of either the lower or higher of the above values, and that range is from the lower to the higher values ​​intended herein (for example, 0.910 to 0.925 or 0.935 g / cm³). 3 For example, 0.912 to 0.925 or 0.915 to 0.918 g / cm³ 3 ). In yet another embodiment, the polymer is 0.945 g / cm³. 3 From 0.970 g / cm³ 3 It may also be a higher density (e.g., HDPE) having a density within the range.

[0054] Furthermore, the rheological properties of the polymer can influence the processing aid composition used to form the molded product. Generally, the PPA composition is preferably used in polymers having a melt index 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. MI or I2 is measured at 190°C and a 2.16 kg load according to ASTM D1238. The melt index ratio (MIR) (MIR is defined herein as the ratio of the high-load melt index (HLMI) (measured per ASTM D1238 at 190°C and a 21.6 kg load) to the melt index, or HLMI / MI) can be 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 polymers of some embodiments. If necessary, the MI in such polymers may be less than 1.5 g / 10 min, such as 1.0 g / 10 min or less (e.g., 0.1, 0.2, or 0.5 g / 10 min to 1.0; or any of 1.1, 1.2, 1.3, 1.4, or less than 1.5 g / 10 min).

[0055] Furthermore, the LLDPE is preferably at least one selected from the group consisting of Ziegler-Natta catalytic LLDPE and metallocene catalytic LLDPE. Metallocene catalytic LLDPE is particularly preferred.

[0056] The thermoplastic resin (B) described above may be crystalline or non-crystalline. If the thermoplastic resin (B) is crystalline, it is preferable that its melting point is 80 to 300°C, and more preferably 100 to 200°C. If the non-crystalline thermoplastic resin (B) is non-crystalline, it is preferable that it has a processing temperature approximately the same as that of the crystalline thermoplastic resin (B) whose melting point range is specified.

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

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

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

[0060] When the dispersed particle size of the above resin (A) is 50 μm or less, the amount of die build-up (DBU) generated is reduced. Therefore, from the viewpoint of suppressing DBU, the dispersed particle size of the above resin (A) is preferably 1 to 50 μm, and more preferably 5 to 30 μm.

[0061] The dispersion particle size of the above resin (A) can be measured by the following method. (1) Using a microtome, cut the thermoplastic resin composition in which resin (A) is dispersed in thermoplastic resin (B) perpendicular to the extrusion direction to a thickness of approximately 30 μm, and collect 10 samples. Heat each of the collected samples to 190°C at a heating rate of 10°C / min, and then let stand for 10 minutes to melt. (2) Observe the molten thermoplastic resin composition using a polarizing 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 one image for each sample, for a total of 10 images, and define the average particle size of the dispersed particles in the images as the dispersed particle size. If the particles are not circular, define the major axis as the particle size.

[0062] The particle size of the dispersed particles of the resin (A) can be adjusted, for example, by the mixing conditions. Specifically, the particle size becomes smaller when the shear force on the object is strong, and larger when the shear force on the object is weak. An example of a method for adjusting the particle size of the dispersed particles of the resin (A) to a range favorable for improving processability is the method for producing the thermoplastic resin composition of this disclosure, which will be described later.

[0063] The thermoplastic resin composition of this disclosure may be a masterbatch, a composition mixed with a masterbatch, or a composition not mixed with a masterbatch, but it is preferable to use a masterbatch or a composition mixed with a masterbatch in order to obtain better processability.

[0064] When the thermoplastic resin composition of this 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 this disclosure is a masterbatch, the melt flow rate (MFR) of the masterbatch is preferably 0.1 g / 10 min or more, more preferably 0.5 g / 10 min or more, even more preferably 1 g / 10 min or more, even more preferably 1.5 g / 10 min or more, and also preferably 100 g / 10 min or less, more preferably 50 g / 10 min or less, even 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 improvement effect on 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, even more preferably 5% by mass or more, particularly preferably 8% by mass or more, and also preferably 80% by mass or less, more preferably 50% by mass or less, even more preferably 40% by mass or less, particularly preferably 30% by mass or less.

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

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

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

[0070] When the thermoplastic resin composition of this disclosure is a composition obtained by mixing with a masterbatch, it is preferable that the composition is a thermoplastic resin composition comprising a masterbatch containing the above resin (A) and the above thermoplastic resin (B), and a thermoplastic resin (C). This provides good processability. In particular, good extrusion processability can be obtained even during long-run molding. Furthermore, the storage stability of the extruded product is also excellent.

[0071] The thermoplastic resin (C) can be the same as the thermoplastic resin (B), and the preferred form is also the same. When the thermoplastic resin composition of this disclosure is a composition mixed with a masterbatch, the thermoplastic resin (B) and the thermoplastic resin (C) may be of the same type or of different types.

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

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

[0074] In this specification, the moisture content is measured by the following method. The thermoplastic resin composition of this disclosure is measured before and after heating at 130°C for 24 hours, and the mass is calculated according to the following formula. Three samples are taken, and the calculation is performed for each sample. The average value is then calculated and adopted. Moisture content (mass%) = [(Mass of thermoplastic resin composition before heating (g)) - (Mass of thermoplastic resin composition after heating (g))] / (Mass of thermoplastic resin composition before heating (g)) × 100

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

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

[0077] The melting point of the polyol described above should be 80°C or lower, but preferably 75°C or lower, more preferably 70°C or lower, even more preferably 68°C or lower, and also preferably 10°C or higher, more preferably 20°C or higher, and even more preferably 25°C or higher. Within the above range, the effect of improving processability will be better.

[0078] The above polyols are, for example, A[(OR 11 ) x Ure 12 ] y It can be expressed as follows, where A is usually an alkylene having one or more ether bonds, and y is 2 or 3, (OR 11 ) x OR is an oxyalkylene group. 11 A poly(oxyalkylene) chain having multiple (x) R 11 Each of these is independently a C2-C5 alkylene, and in some embodiments, it is a C2-C3 alkylene, R 12 is hydrogen, alkyl, aryl, arylalkenyl, alkylallyrenyl, -C(O)-alkyl, -C(O)-aryl, -C(O)-arylalkenyl or -C(O)-alkylallyrenyl, where -C(O)- is OR 12 It is bonded to O. x is between 10 and 230,000.

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

[0080] The above polyol consists of chains of randomly distributed oxyalkylene groups (e.g., copolymer units of -OC2H4- and -OC3H6-), or alternating blocks consisting of repeating oxyalkylene groups (e.g., (-OC2H4-) a1 Block and (-OC3H6-) b1 It can also be a polymer containing blocks, and a1+b1 can be a chain having 10 to 230,000 units.

[0081] In some embodiments of the above polyols, 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 These are hydrogen, methyl, butyl, phenyl, benzyl, acetyl, benzoyl, or stearyl.

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

[0083] The above polyols may be used individually or in combination of two or more. Polyethylene glycol and polyethylene oxide are preferred, with polyethylene glycol being particularly preferred, due to their excellent effect in improving processability.

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

[0085] The viscosity-average molecular weight (Mv) of the polyethylene oxide is preferably 100,000 or more, more preferably 120,000 or more, even more preferably 140,000 or more, and also preferably 10,000,000 or less, more preferably 1,600,000 or less, and even more preferably 500,000 or less. Within the above range, the improvement effect on 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, and the polymer concentration c, [η] is calculated by extrapolating the polymer concentration c to 0. Inserting [η] into the following formula, the viscosity-average molecular weight M is calculated. Formula: [η] = 6.4 × 10 -5 M 0.82

[0086] The polycaprolactone described above may be a homopolymer of ε-caprolactone or a modified polycaprolactone. Examples of the modified polycaprolactone include those obtained by modifying ε-caprolactone in the presence of 1,4-butanediol or the like during ring-opening polymerization, or those obtained by modifying the ends of the polymer with ether or ester groups.

[0087] The weight-average molecular weight (Mw) of the above polycaprolactone is preferably 2,000 or more, more preferably 10,000 or more, even more preferably 25,000 or more, and also preferably 100,000 or less, more preferably 95,000 or less, and even more preferably 90,000 or less. Within the above range, the improvement effect on processability is better. In this specification, the weight-average molecular weight is measured by gel permeation chromatography (GPC) on a polystyrene basis.

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

[0089] The above silicones can, in principle, be any organosilicon compounds known to those skilled in the art by the term silicone polymers. A proper definition of silicone can be found in Winnacker / Kuchler: "Chemical Technology", edited by R. Dittmeyer, W. Keim, G. Kreysa, and A. Oberholz, Vol. 5: "Organic Intermediates, Polymers", Chapter: "Silicones", Wiley-VCH, Weinheim, 2005.

[0090] The 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 of various silicone polymers can also be used. As already mentioned, silicone-containing copolymers, such as polyether-functionalized silicones, silicone block copolymers with silicones or organic polymers containing urea or urethane units, can also be used. For better additiveity, the use of high molecular weight polydiorganosiloxanes is particularly preferred, which may also contain non-silicone components, such as fillers like fine particle silicic acid, chalk, talc, and sheet-like silicates.

[0091] Preferably, the silicone polymer corresponds to formula A, and [R 13 3SiO 1 / 2 ] a2 [SiR 13 20 2 / 2 ] b2 [R 13 SiO 3 / 2 ] c2 [SiO 4 / 2 ] d2 , here R 13 a2, b2, c2, and d2 are hydrogen, -OH, or unsubstituted or substituted C1 to C18 hydrocarbon residues, a2, b2, c2, and d2 each represent 0 or an integer, and a2+b2+c2+d2 is an integer from 5 to 15000.

[0092] C1 to C18 hydrocarbon residues R 13Examples of alkyl residues include methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, and tert-pentyl residues; hexyl residues, such as n-hexyl residues; heptyl residues, such as n-heptyl residues; octyl residues, such as n-octyl 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, cyclohexyl, 4-ethylcyclohexyl and cycloheptyl residues; norbornyl and methylcyclohexyl residues. Among alkyl residues, C1 to C6 residues, such as methyl and ethyl residues, with methyl residues being particularly preferred.

[0093] R 13 Examples also include unsaturated C1 to C18 hydrocarbon residues, e.g., alkenyl residues, e.g., 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, e.g., phenyl residues, biphenylyl residues, and naphthyl residues; alkaryl residues, e.g., o-, m-, and p-tolyl residues, and phenethyl residues (2-phenylethyl residues, 1-phenylethyl residues); and aralkyl residues, e.g., benzyl residues. Preferred unsaturated C1 to C18 hydrocarbon residues R 13 These are vinyl residues and phenyl residues.

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

[0095] residue R 13 Preferably, it bonds to the silicone polymer represented by formula A via Si-C bonds, but it can also bond to the silicone polymer via oxygen atoms -O-.

[0096] R 13 It preferably has 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, and particularly preferably at most 7000.

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

[0099] Preferably, all residues R 13 At least 50%, more preferably at least 70%, and especially preferably at least 80% of the residues are methyl residues.

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

[0101] Among silicones, silicone polymers having a very high molecular weight, for example, UHMW polysiloxane (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 is in the range of >1000 to about 14000, which corresponds to a number average molecular weight between 74 kg / mol and 1000 kg / mol.

[0103] Typical UHMW polysiloxane preferably has 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 description of viscosity represents the arithmetic mean value of three individual measurement values carried out independently.

[0104] Among the above UHMW polysiloxanes, high molecular weight polydimethylsiloxane 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) is particularly preferred because it is inexpensive and effective.

[0105] The above UHMW polysiloxanes include commercially available UHMW polysiloxanes such as MULTIBASE® MB50-001 and MULTIBASE® MB50-002 from Dupont, and GENIOPLAST® PELLET S, GENIOPLAST® PELLET P PLUS, GENIOPLAST® PE50S08, GENIOPLAST® PP50S12 and mixtures thereof from Asahi Kasei Wacker Silicone Co., Ltd., with MB50-002 and GENIOPLAST® PELLET S being preferred.

[0106] Silicone polymers are commercially available in pellet / granule or masterbatch form for immediate use, and can, for example, be mixed with thermoplastic granules before further processing.

[0107] The above-described polyamide-polyether block copolymer is a copolymer having polyamide blocks and polyether blocks in its polymer backbone. In this disclosure, such a block copolymer having polyamide blocks and polyether blocks may also be called a "polyamide / polyether block copolymer." It can also be abbreviated as "PEBA copolymer" or "PEBA." In some embodiments of this disclosure, the PEBA copolymer can be represented by the following general formula. [ka]

[0108] Here, PA represents the length of the polyamide block, PE represents the length of the polyether block, and p represents the total number of polyamide and polyether blocks. In some embodiments of this disclosure, the polyether block can be represented by the following general formula. [ka]

[0109] Here, EG is the first unspecified terminal group, B is the unspecified crosslinking group, and EG * This is the second unspecified terminal group, EG, B and EG * The length is 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, and p represents the length of the PEBA copolymer and the total number of polyamide and polyether blocks. In some embodiments of this disclosure, the PEBA copolymer can be represented by the following general formula. [ka]

[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 the total number of polyamide and polyether blocks is shown.

[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 a PEBA copolymer can be measured, for example, by gel permeation chromatography (i.e., size exclusion chromatography) using narrow molecular weight polymer standards with techniques known in the art.

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

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

[0115] In embodiments, the weight-average molecular weight Mw of the PEBA copolymer is 25,000 to 500,000 g / mol, including subranges 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 about 100,000 to about 250,000 g / mol, or about 100,000 to about 150,000 g / mol, or about 125,000 to about 150,000 g / mol. The polyamide and polyether blocks within the PEBA copolymer described above can be randomly distributed.

[0116] The above PEBA copolymer comprises a polyamide block and a polyether block, the polyamide block may account for at least 50% by mass of the copolymer. Furthermore, the PEBA copolymer comprises 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-mentioned polyamide and polyether block precursors, PEBA copolymers having polyamide blocks and polyether blocks can be prepared. For example, by reacting a lactam, a polyetherdiol, and a chain-limiting diacid together in the presence of a small amount of water, a PEBA copolymer having polyamide blocks and polyether blocks of variable length and statistically random distribution within the block copolymer chain can be obtained. The above polyether blocks may be derived from poly(oxyethylene), poly(oxypropylene), or poly(tetramethylene ether) glycol, each of which may spontaneously co-condense with a polyamide block containing carboxylic acid chain ends. Chain limiting agents may also be present during the polycondensation reaction to give a PEBA copolymer containing polyamide and polyether blocks randomly distributed within the block copolymer. The above polyether blocks are derived from poly(oxyethylene), poly(oxypropylene), or poly(tetramethylene ether) glycols, which are first converted to polyetherdiamines by amination and then co-condensed with polyamide blocks containing carboxylic acid chain ends. Chain limiting agents are also present during the polycondensation reaction to give a PEBA copolymer containing polyamide 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 blocks 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 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 PEBA copolymer comprises 10 to 20 polyamide blocks and 10 to 20 polyether blocks.

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

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

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

[0124] The above PEBA copolymer comprises i) a polyamide block which is polyamide-12 (PA-12) and ii) a polyether block which is polyethylene glycol (PEG), where 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 PEBA copolymer comprises 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 PEBA copolymer comprises i) a polyamide block which is polyamide-12 (PA-12), and ii) a polyether block which is polyethylene glycol (PEG), with a number average molecular weight Mn of approximately 25,000 to approximately 75,000 g / mol.

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

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

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

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

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

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

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

[0134] The above PEBA copolymer comprises i) a polyamide block which is polyamide-11 (PA-11), 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 polytetrahydrofuran (PTHF).

[0135] The above PEBA copolymer comprises 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 approximately 75% to 10% by mass of the copolymer, and the polytetrahydrofuran block represents approximately 25% to 90% by mass of the copolymer.

[0136] The above PEBA copolymer comprises 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 about 80% to 60% by weight of the copolymer, and the polytetrahydrofuran block represents about 20% to 40% by weight of the copolymer.

[0137] The above PEBA copolymer comprises 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 about 40% to 60% by mass of the copolymer, and the polytetrahydrofuran block represents about 60% to 40% by mass of the copolymer.

[0138] The above PEBA copolymer comprises 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 approximately 30% to 10% by mass of the copolymer, and the polytetrahydrofuran block represents approximately 70% to 90% by mass of the copolymer. The above PEBA copolymer comprises 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 PEBA copolymer comprises 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 approximately 25,000 to approximately 75,000 g / mol. The above PEBA copolymer comprises i) a polyamide block which is polyamide-12 (PA-12) and ii) a polyether block which is polytetrahydrofuran (PTHF), with a number average molecular weight Mn of about 40,000 to about 60,000 g / mol. In embodiments 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 polytetrahydrofuran (PTHF), with a number average molecular weight Mn of about 50,000 g / mol.

[0140] The above PEBA copolymer comprises i) a polyamide block which is polyamide-6 (PA-6), and ii) a polyether block which is polytetrahydrofuran (PTHF). The above PEBA copolymer comprises 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 sold under the trade name PEBAX®.

[0141] The above 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 Examples include SA 01 MED, PEBAX MV 5533 SP01, PEBAX MV 5533, PEBAX MV 5533 SP01, PEBAX RNEW (registered trademark) 30R51 SA 01, PEBAX RNEW 35R53 SP01, PEBAX 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 trademark names VESTAMID® or VESTAMID E.

[0142] The above 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 these, Pebax MV1072 is preferred.

[0143] The above 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 may include, for example, anti-sticking agents; UV absorbers; flame retardants; reinforcing materials such as glass fibers and glass powder; stabilizers such as minerals and flakes; lubricants such as silicone oil and molybdenum disulfide; pigments such as titanium dioxide and red iron oxide; conductive agents such as carbon black; impact-resistant agents such as rubber; antioxidants such as hindered phenols and phosphorus-based antioxidants; and nucleating agents and antiblocking agents such as metal salts and sorbitol acetals.

[0145] The thermoplastic resin composition of this disclosure is obtained, for example, by a manufacturing method that includes a mixing step of mixing resin (A) and thermoplastic resin (B) using a twin-screw extruder. This makes it possible to adjust the dispersed particle size of resin (A) to a range favorable for improving processability. This disclosure also relates to a method for manufacturing the above-described thermoplastic resin composition, including the mixing step.

[0146] By using a twin-screw extruder, the materials can be mixed (kneaded) while applying shear force, making it easy to adjust the particle size of the resin (A) mentioned above. In this case, melt kneading is preferable. When performing melt-mixing, each component may be melted during the mixing process, or it may be melted before the mixing process.

[0147] The twin-screw extruder described above comprises a screw with multiple screw elements, each containing two or more kneading disc elements, mounted on a shaft, and a barrel containing two of these screws. Preferably, the kneading area ratio, which is the total length of the kneading disc elements divided by the total length of the screws, is 0.01 or more. The units for the total length of the kneading disc elements and screws are usually in millimeters.

[0148] The twin-screw extruder described above comprises, for example, two screws, a barrel containing the two screws, a raw material supply port provided in the barrel, and a die provided at the downstream end of the barrel. A vacuum vent provided in the barrel may be further provided as needed.

[0149] The above-mentioned twin-screw extruder may be a co-rotating twin-screw extruder in which two screws passed through a cylinder of a barrel with an inverted V-shaped through hole are rotated in the same direction, or it may be an anti-rotating extruder in which the two screws are rotated in opposite directions.

[0150] As the above-mentioned twin-screw extruder, a co-rotating twin-screw extruder is preferred because it excels in conveying capacity, melting and kneading capacity, and separation (dewatering) capacity, as well as enabling continuous material processing and improving the efficiency of the resin composition manufacturing process.

[0151] The meshing of the two screws described above may be non-meshing, partially meshing, or fully meshing.

[0152] The screw used is one that allows the kneading area, described later, to be incorporated at any position on the screw. Therefore, the screw used is one in which multiple screw elements, including two or more kneading disc elements, are mounted on a shaft.

[0153] Screw elements have the same cross-sectional shape in the direction perpendicular to the axis. In screw elements, a unique function arises depending on the number of flights and the twist angle at which the cross-sectional shape perpendicular to the axis rotates around the shaft. Examples of screw elements, depending on their function, include rotary elements, kneading disc elements, and mixing elements.

[0154] A rotary element is a screw element with a torsional angle that rotates continuously around a shaft and has conveying capabilities.

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

[0156] The mixing element is a screw element formed by creating a notch in a right-hand threaded full-flight element, or a screw element formed by creating a notch in a left-hand threaded full-flight element. The mixing element may or may not have self-cleaning properties.

[0157] The screw of the twin-screw extruder described above preferably consists of a rotary element, a kneading disc element, and a mixing element.

[0158] In the above twin-screw extruder, the kneading area ratio is preferably 0.02 or higher, more preferably 0.05 or higher, even more preferably 0.10 or higher, particularly preferably 0.15 or higher, and most preferably 0.20 or higher. Furthermore, the kneading area ratio is preferably 0.45 or lower, and more preferably 0.30 or lower. If the kneading area ratio is above the lower limit, the resin (A) is well dispersed in the thermoplastic resin (B), and an excellent processability improvement effect is easily achieved. If the kneading area ratio is below the upper limit, excessive shear heat generation and internal heat generation due to deformation and compression on the thermoplastic resin A or B by the screw are suppressed, and excessive decomposition of the thermoplastic resin A or B is prevented.

[0159] When the kneading area ratio is 0.10 or higher, the dispersed particle size of the resin (A) tends to be 1 to 100 μm, and it tends to show an excellent improvement in processability. When the kneading area ratio is 0.15 or higher, the dispersed particle size of the resin (A) tends to be 1 to 50 μm, and it tends to show an even better processability improvement effect.

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

[0161] When the thermoplastic resin composition of this disclosure is a masterbatch and the dispersed particle size of the resin (A) is 50 μm or less, it is preferable that the "kneading area ratio" × "concentration (mass%) of resin (A) in the masterbatch" is 3.1 to 8.5 in order to reduce the amount of die build-up (DBU).

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

[0163] Preferably, the twin-screw extruder has one or more molten zones in which at least one of the mixing element and kneading disc element of the screw element is arranged in a continuous sequence of two or more. The presence of a molten zone in the twin-screw extruder allows the resin (A) and thermoplastic resin (B), etc., to be melted and kneaded. Because the twin-screw extruder has a molten zone, the residence time of the resin (A) and thermoplastic resin (B), etc., in the twin-screw extruder is increased by at least one of the mixing element and kneading disc element arranged in a continuous sequence of two or more. When the resin (A) and thermoplastic resin (B), etc., pass through the molten zone, shear heat is applied to the resin (A) and thermoplastic resin (B), etc., by the screw, causing the resin (A) and thermoplastic resin (B), etc., to become molten. This improves the adhesion between the resin (A) and thermoplastic resin (B), etc., and the screw, and suppresses the occurrence of vent-up.

[0164] The number of molten zones is preferably one or two, and more preferably one. If the number of molten zones is two or less, the shear heat generation or deformation compression action of resin (A) and thermoplastic resin (B) by the screw is suppressed, and excessive decomposition of resin (A) and thermoplastic resin (B) is suppressed.

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

[0166] The barrel block has through holes formed in it that correspond to the cross-sectional shape of the screw.

[0167] A vacuum vent is installed to remove low-boiling-point components contained in resin (A) and thermoplastic resin (B) when they are melted and kneaded by the screw of a twin-screw extruder.

[0168] A vacuum vent can be installed in a twin-screw extruder, for example, by using a barrel block equipped with a vacuum vent. Multiple vacuum vents may be provided on the barrel blocks.

[0169] If there is only one raw material supply port, it is located upstream of the upstreammost kneading area. If there are multiple raw material supply ports, the first raw material supply port, which is the most upstream of the raw material supply ports, may be located upstream of the most upstream kneading area, while the other raw material supply ports may be located downstream of the most upstream kneading area. It is preferable that resin (A) and thermoplastic resin (B) are supplied from the first raw material supply port. Components other than resin (A) and thermoplastic resin (B) may be supplied from the second raw material supply port or later.

[0170] When pelletizing a compound, it is preferable to use a die that can extrude the compound to form strands.

[0171] The number of discharge ports in the die may be one or multiple. A die with several to several dozen discharge ports is preferred because it allows for the formation of multiple strands, resulting in good productivity.

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

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

[0174] The above-mentioned twin-screw extruder may be used for mixing when manufacturing a masterbatch, or for other mixing processes, but it is preferable to use it for mixing when manufacturing a masterbatch. Furthermore, the above-mentioned twin-screw extruder may be used in combination with other mixers; for example, after manufacturing a masterbatch with the above-mentioned twin-screw extruder, the masterbatch may be mixed with the thermoplastic resin using another mixer.

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

[0176] In the method for producing the thermoplastic resin composition of this disclosure, after the mixing step, an extrusion step in which the mixture is extruded and a molding step in which the extruded material is molded using a molding machine or the like may be performed.

[0177] The molding process described above is not particularly limited and can include, for example, extrusion molding, injection molding, blow molding, etc., but among these, extrusion molding is preferred in order to effectively exhibit the above-mentioned moldability.

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

[0179] The above-mentioned conditions for molding are not particularly limited and can be set as appropriate depending on the composition and quantity of the composition, the desired shape and size of the molded product, etc.

[0180] <Molded body> The molded articles of this disclosure are made using the thermoplastic resin composition of this disclosure, and may be obtained, for example, by a molding process that molds the thermoplastic resin composition of this disclosure. This disclosure also relates to a method for manufacturing the molded article of this disclosure, including a molding process. The thermoplastic resin compositions of this disclosure are suitable for molded articles in the form of tubes, films, or sheets, but can also be applied to molded articles of other shapes.

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

[0182] In the molding process described above, the molding temperature (extrusion temperature) is generally set to a temperature above the melting point of the thermoplastic resin (B) and below the decomposition temperature of the resin (A). A temperature range of 160°C to 270°C is preferable for the processing aid to exert its effects most effectively. The molding temperature mentioned above is sometimes referred to as the extrusion temperature in the case of extrusion molding.

[0183] The applications of the molded articles of this disclosure are not particularly limited, but include, for example, bags, coverings, tableware such as beverage containers, electric wires, cables, pipes, fibers, bottles, gasoline tanks, and various other industrial molded products.

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

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

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

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

[0188] Although embodiments have been described above, it should be understood that various modifications to the form and details are possible without departing from the spirit and scope of the claims. [Examples]

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

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

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

[0192] Here, we will explain in more detail the twin-screw extruder used in the melt-mixing process. Figure 1 is a schematic diagram showing the twin-screw extruder used in the melt-mixing process. The twin-screw extruder 10 comprises 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 comprises, in order from the upstream side, the first barrel block C1 to the fifteenth barrel block C15. The raw material supply port 16 is located in the first barrel block C1. The twin-screw extruder 10 has a melting zone (not shown) extending from a portion of the 6th barrel block C6 to a portion of the 13th barrel block C13. All screw elements outside the molten zone are rotary elements. The molten zone consists of two or more kneading disc elements. The number of kneading disc elements was set so that the kneading area ratio would be the values ​​shown in Tables 1 and 2.

[0193] Next, the dispersion particle size of resin (A) in the obtained masterbatch was evaluated using the dispersion evaluation method described below. The results are shown in Tables 1 and 2. Next, the obtained masterbatch was dry-blended with a matrix resin (thermoplastic resin (C)) at a ratio such that the concentration of resin (A) in the final thermoplastic resin composition was constant (2000 ppm), and the processability at that time was evaluated by the extrusion evaluation described below. The results are shown in Tables 1 and 2. Furthermore, since none of the resins used (A), thermoplastic resin (C), and thermoplastic resin (B) contain fluorine, the fluorine content in the manufactured masterbatch and thermoplastic resin composition was 0% by mass.

[0194] <Variable Evaluation> (1) Using a microtome, cut the masterbatch in which the resin (A) is dispersed in the thermoplastic resin (B) perpendicular to the extrusion direction to a thickness of approximately 30 μm, and collect 10 samples. Heat each of the collected samples to 190°C at a heating rate of 10°C / min, and then let stand for 10 minutes to melt. (2) Observe the molten thermoplastic resin composition using a polarizing 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 one image for each sample, for a total of 10 images, and define the average particle size of the dispersed particles in the images as the dispersed particle size. If the particles are not circular, define the major axis as the particle size.

[0195] <Extrusion Evaluation> Each material was extruded for 60 minutes using a single-screw extruder (HAAKE Rheomex OS, L / D: 33, screw diameter: 20 mm, die diameter: 2 mm) under the following conditions: cylinder temperature 170-200°C, die temperature 200°C, and shear rate 450 / second. The following items were evaluated. Prior to each test run, 15% by mass of silica-containing linear low-density polyethylene was placed in the hopper, the screw rotation speed was increased to 150 rpm, and purging was performed for approximately 15 minutes. Next, the same matrix resin to be used in the test was placed in, and purging was performed for approximately 15 minutes. After that, 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 procedure was repeated until the initial pressure returned before the next experiment was conducted. (Melt Fracture (MF) disappearance time) Extrusion was performed using only the matrix resin, with melt fracture occurring throughout the entire surface, until the pressure stabilized. The point at which the screw became visible was defined as zero, and extrusion continued for 60 minutes. In cases where processing aids or masterbatches were used, these were added to the hopper at the zero point. The appearance of the strands at the beginning of extrusion and at the completion of extrusion was checked visually and by touch. The time from the zero point described above until the MF observed at the beginning of extrusion disappeared was measured. A shorter time indicates better performance. If the MF did not disappear, it was indicated with "-". (Dyne Build-Up (DBU)) For samples in which MF (microfiltrate) had completely disappeared, extrusion evaluation was performed using a long-run molding process (3 hours). The condition of the die after extrusion was visually checked, and the presence or absence of DBU (die discharge) was evaluated. The evaluation was based on a 5-point scale from 1 to 5. A lower value indicates less DBU (Deep Burden Occurrence) and better results, while a value of 1 indicates no DBU occurred.

[0196] [Table 1]

[0197] [Table 2] [Explanation of symbols]

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

Claims

1. A masterbatch comprising resin (A) and thermoplastic resin (B), and thermoplastic resin (C), wherein resin (A) comprises structural units represented by the following formula 1, and the dispersed particle size of resin (A) is 1 to 100 μm. The content of the aforementioned resin (A) is 0.1 to 1.0% by mass, A thermoplastic resin composition in which the thermoplastic resin (B) is a polyolefin resin. -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 composed of at least one selected from the group consisting of X1 and X2, X1 is a group composed of 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). X2 is an aromatic hydrocarbon group having 1 to 12 carbon atoms, which may have substituents. Y and Z are each independently composed of at least one group selected from the group consisting of a single bond, -O-, -C(=O)-, -C(=O)O-, 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 are each independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, n and m are each independent integers between 0 and 10. At least one of X, Y, and Z is -C(=O)-, -C(=O)O-, or -C(OR')R'-.

2. A thermoplastic resin composition according to claim 1 that is substantially free of fluorine.

3. The thermoplastic resin composition according to claim 1 or 2, wherein X is a divalent group 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).

4. The thermoplastic resin composition according to claim 1 or 2, wherein Y and Z in formula 1 are each independently composed of at least one group selected from the group consisting of a single bond, -O-, -C(=O)-, and -C(=O)O-.

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

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

7. The thermoplastic resin composition according to claim 1 or 2, wherein the thermoplastic resin (B) is polyethylene.

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

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

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

11. The molded article according to claim 10, which is tubular, film-like, or sheet-like.

12. A method for producing a thermoplastic resin composition according to claim 1 or 2, comprising a mixing step of mixing the resin (A) and the thermoplastic resin (B) using a twin-screw extruder.

13. The twin-screw extruder comprises a screw having multiple screw elements, including two or more kneading disc elements, mounted on a shaft, and a barrel containing two of the screws. A method for producing a thermoplastic resin composition according to claim 12, wherein the kneading area ratio, which is the value obtained by dividing the total length of the kneading disc element by the total length of the screw, is 0.01 or more.

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