Processing aids, masterbatches, thermoplastic resin compositions and molded articles, and methods for producing the same.

Abstract

To provide a processing aid and a master batch which can improve processibility of a thermoplastic resin, a thermoplastic resin composition and a molded body using them, and a method for manufacturing them.SOLUTION: A processing aid has surface free energy of 28.5 mN / m or more, and does not substantially contain fluorine.SELECTED DRAWING: None

Description

Technical Field

[0001] The present disclosure relates to processing aids, masterbatches, thermoplastic resin compositions and molded articles, and methods for producing them.

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 where the surface becomes rough, called melt fracture, occurs, 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 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 processing aid and a masterbatch that can improve the processability of thermoplastic resins, a thermoplastic resin composition and a molded article using them, and methods for producing them.

Means for Solving the Problems

[0006] The present disclosure (1) is a processing aid having a surface free energy of 28.5 mN / m or more and substantially free of fluorine.

[0007] The present disclosure (2) is the processing aid according to the present disclosure (1) having a surface free energy of 29.0 to 55.0 mN / m.

[0008] The present disclosure (3) is the processing aid according to the present disclosure (1) or (2) containing a structural unit represented by the following formula 1. -X-(CR 1 R 2 ) n -Y-(CR 3 R 4 ) m -Z- (Formula 1) [[ID=*]]{"ID": 23, "translation": " "} [[ / ID]] (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 及び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, at least one of X, Y and Z is -C(=O)-, -C(=O)O-, -OC(=O)O- or -C(OR’)R’-.)

[0009] In the present disclosure (4), in the formula 1, X is X 1 and X 2A 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 The processing aid described in (3) of this disclosure is an aromatic hydrocarbon group having 1 to 12 carbon atoms, which may have substituents.

[0010] The present disclosure (5) is a processing aid according to the present disclosure (4), wherein X in formula 1 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).

[0011] The present disclosure (6) is a processing aid according to any one of the present disclosures (3) to (5), wherein in formula 1, Y and Z are each independently 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).

[0012] The present disclosure (7) is a processing aid according to the present disclosure (6), 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-.

[0013] Disclosure (8) is a processing aid according to any of Disclosures (1) to (7), wherein the melt flow rate at 190°C and a load of 2.16 kgf is 0.001 to 100 g / 10 min.

[0014] Disclosure (9) is a processing aid according to any one of Disclosures (1) to (8), which is at least one selected from the group consisting of polybutylene adipate terephthalate, polybutylene succinate, polylactic acid, and ethylene vinyl alcohol copolymer.

[0015] Disclosure (10) is a masterbatch comprising a processing aid described in any of Disclosures (1) to (9) and a thermoplastic resin (A).

[0016] This disclosure (11) is the masterbatch according to this disclosure (10), wherein the thermoplastic resin (A) is a polyolefin resin.

[0017] Disclosure (12) is a masterbatch according to Disclosure (10) or (11), wherein the thermoplastic resin (A) is metallocene-catalyzed linear low-density polyethylene.

[0018] Disclosure (13) is a masterbatch according to any one of Disclosures (10) to (12), wherein the difference in surface free energy between the processing aid and the thermoplastic resin (A) is 1.5 mN / m or more.

[0019] The present disclosure (14) is a masterbatch according to any of the present disclosures (10) to (13), wherein the difference in surface free energy between the processing aid and the thermoplastic resin (A) is 4.0 to 45 mN / m.

[0020] (15) This disclosure is a masterbatch according to any of (10) to (14) of this disclosure, wherein the mass ratio of the thermoplastic resin (A) and the processing aid (thermoplastic resin (A): processing aid) is 92:8 to 70:30.

[0021] Disclosure (16) is a thermoplastic resin composition comprising a processing aid described in any of Disclosures (1) to (9) and / or a masterbatch described in any of Disclosures (10) to (15), and a thermoplastic resin (B).

[0022] The present disclosure (17) is a thermoplastic resin composition according to the present disclosure (16), wherein the thermoplastic resin (B) is a polyolefin resin.

[0023] The present disclosure (18) is a thermoplastic resin composition according to the present disclosure (16) or (17), wherein the thermoplastic resin (B) is metallocene-catalyzed linear low-density polyethylene.

[0024] The present disclosure (19) is a thermoplastic resin composition according to any one of the present disclosures (16) to (18), wherein the difference in surface free energy between the processing aid and the thermoplastic resin (B) is 1.5 mN / m or more.

[0025] The present disclosure (20) is a thermoplastic resin composition according to any one of the present disclosures (16) to (19), wherein the difference in surface free energy between the processing aid and the thermoplastic resin (B) is 4.0 to 45 mN / m.

[0026] Disclosure (21) is a thermoplastic resin composition according to any one of Disclosures (16) to (20), wherein the content of the processing aid is 0.1 to 1.0% by mass.

[0027] Disclosure (22) is a molded article using a thermoplastic resin composition described in any of Disclosures (16) to (21).

[0028] The present disclosure (23) is a molded article according to the present disclosure (22), which is in the form of a tube, a film, or a sheet.

[0029] This disclosure (24) is a method for producing a processing aid according to any of the disclosures (1) to (9), including a mixing step and a dispensing step.

[0030] This disclosure (25) is a method for producing a masterbatch according to any of this disclosure (10) to (15), including a mixing step and a dispensing step.

[0031] This disclosure (26) is a method for producing a thermoplastic resin composition according to any one of this disclosure (16) to (21), including a mixing step and an extrusion step.

[0032] This disclosure (27) is a method for manufacturing a molded article according to this disclosure (22) or (23), including a molding step. [Effects of the Invention]

[0033] According to this disclosure, it is possible to provide processing aids and masterbatches that can improve the processability of thermoplastic resins, thermoplastic resin compositions and molded articles using these, and methods for manufacturing these. [Modes for carrying out the invention]

[0034] The following provides a detailed explanation of this disclosure.

[0035] <Processing aid> The processing aids of this disclosure have a surface free energy of 28.5 mN / m or more and are substantially free of fluorine.

[0036] The processing aids disclosed herein provide good processability (particularly extrusion processability). The processing aids disclosed herein were developed based on the discovery that there is a strong correlation between surface free energy and processability, and that particularly good processability is obtained when the surface free energy is within a specific range.

[0037] The processing aid of this disclosure preferably has a surface free energy of 28.6 mN / m or more, more preferably 29.0 mN / m or more, preferably 55.0 mN / m or less, more preferably 50.0 mN / m or less, even more preferably 45.0 mN / m or less, even more preferably 40.0 mN / m or less, and especially preferably 35.0 mN / m or less. The surface free energy can be calculated using the method described in the examples.

[0038] The processing aids of this disclosure are 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). It is particularly preferable that the processing aids of this disclosure are fluorine-free (the fluorine content is 0% by mass).

[0039] The processing aid of this disclosure preferably contains a structural unit represented by the following formula 1, and more preferably is a polymer containing a structural unit represented by the following formula 1. -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'-.

[0040] When the processing aid of this disclosure is the polymer described above, the surface free energy changes depending on the terminal molar ratio in the processing aid, which is calculated by the calculation method described below. A higher terminal content increases the surface free energy, and a lower terminal content decreases the surface free energy. The terminal molar ratio of the processing aid of this disclosure is preferably 0.00001 to 0.00450 mol%. Calculation method: When the amount of polymer (g) is 1g, Monomer amount (mol) = 1g / Molecular weight of monomer (g / mol) Number of monomers (amounts) = Amount of monomer (moles) × 6.02 × 10^23 Here, when the number-average molecular weight of the polymer is Mn, Number of polymer strands = Number of monomers / Mn Number of polymer ends = Number of polymer strands × 2 Number of end-cell moles (moles) = Number of polymer end-cells (units) / 6.02 × 10^23 Terminal molar ratio (mol%) = Number of terminal moles (mol) / Amount of monomer (mol)

[0041] The terminal molar ratio changes depending on the oligomers (components with a molecular weight of 5000 g / mol or less) in the processing aid; an increase in the amount of oligomers increases the terminal molar ratio, and a decrease in the amount of oligomers decreases the terminal molar ratio. The amount of oligomers can be reduced by purification methods such as dissolving the polymer in a good solvent and then collecting the precipitate generated by dropping it into a poor solvent.

[0042] 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 2It is preferably an aromatic hydrocarbon group having 1 to 12 carbon atoms, which may have substituents.

[0043] 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).

[0044] 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.

[0045] 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).

[0046] 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-.

[0047] In formula 1 above, R 1 , R 2 , R 3 and R 4 Each 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.

[0048] 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.

[0049] Furthermore, the polymer may contain structural units other than those represented by Formula 1. Examples of structural units other than those 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.

[0050] In the processing aid of this disclosure, the content of the structural unit represented by Formula 1 is preferably 0.1% by mass or more, more preferably 1% by mass or more, even more preferably 10% by mass or more, and particularly preferably 20% by mass or more. It is also preferably 99.9% by mass or less, more preferably 99% by mass or less, and even more preferably 95% by mass or less.

[0051] Examples of the above processing aids include polybutylene adipate terephthalate (PBAT), polylactic acid (PLA), polybutylene succinate (PBS), polybutylene succinate adipate (PBSA), and ethylene-vinyl alcohol copolymer (EVOH). Preferably, the above processing aid is at least one selected from the group consisting of PBAT, PLA, PBS, and EVOH; more preferably, it is at least one selected from the group consisting of PBAT, PLA, PBS, and EVOH; and even more preferably, it is at least one selected from the group consisting of PLA and EVOH. Furthermore, it is preferable that the processing aid is not polyethylene glycol (PEG).

[0052] 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.

[0053] 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.

[0054] The degree of saponification of the above ethylene-vinyl alcohol copolymer is preferably 80 to 100 mol%.

[0055] 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.

[0056] 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.

[0057] The melting point of the above processing aid is preferably 65°C or higher, more preferably 70°C or higher, even more preferably 75°C or higher, and 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 will be 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.

[0058] The melt flow rate (MFR) of the above processing aid 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, particularly preferably 0.5 g / 10 min or more, and 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 100 g / 10 min or less, even more preferably 40 g / 10 min or less, especially preferably 20 g / 10 min or less, particularly preferably 10 g / 10 min or less. Within the above range, the processability improvement effect will be 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.

[0059] The processing aid of this disclosure may be a mixture of the above-described component (component A) and another component (component B). Other components include synergists, which are 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.

[0060] 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.

[0061] The above polyols are, for example, A[(OR 11 ) x2 Ure 12 ] y2 It can be expressed as follows, where A is usually an alkylene having one or more ether bonds, and y2 is 2 or 3, (OR 11 ) x2 OR is an oxyalkylene group. 11 A poly(oxyalkylene) chain having multiple (x2) R 11Each 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. x² is between 10 and 230,000.

[0062] 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-.

[0063] 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.

[0064] 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.

[0065] The above polyol is a dicarboxylic acid and A[(OR 11 ) x2 Ure 12 ] y2A 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.

[0066] 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.

[0067] 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.

[0068] 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

[0069] 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.

[0070] 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.

[0071] 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 even more 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.

[0072] 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.

[0073] 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.

[0074] 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.

[0075] 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.

[0076] 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.

[0077] 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.

[0078] 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-.

[0079] R 13 It preferably has 1 to 6 carbon atoms. Ethyl residues, phenyl residues, vinyl residues, and methyl residues are particularly preferred.

[0080] 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.

[0081] Preferably, c² + d² means < 0.1 × (a² + b² + c² + d²), and in particular, c² + d² < 0.05 × (a² + b² + c² + d²).

[0082] 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.

[0083] 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.

[0084] Among silicones, silicone polymers with very high molecular weights, such as UHMW polysiloxane (ultra-high molecular weight; described by KJRyan et al., Journal of Vinyl & Additive Technology, March 2000, Vol. 6, No. 1, pp. 7 to 19), may also be used.

[0085] The degree of polymerization of UHMW polysiloxanes ranges from >1000 to approximately 14000, which corresponds to a number-average molecular weight between 74 kg / mol and 1000 kg / mol.

[0086] Typical UHMW polysiloxanes have a dynamic viscosity between 10 kPa.s and 50 kPa.s, preferably between 15 kPa.s and 30 kPa.s, measured with an airborne rotational rheometer according to DIN EN ISO 3219:1994 and DIN 53019, using a plate-plate system (25 mm diameter) with a 0.5 mm measurement gap. The measurement temperature is 25.00 °C ± 0.1 °C. The shear rate gradient is 0.1 sec. -1 The viscosity value is the arithmetic mean of three independent measurements.

[0087] Because it is 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, and particularly preferably between 15 and 30 kPa.s (preferably measured by the method described above) are particularly preferred.

[0088] 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.

[0089] 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.

[0090] 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]

[0091] 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]

[0092] 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]

[0093] 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.

[0094] 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).

[0095] 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.

[0096] 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.

[0097] 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.

[0098] 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.

[0099] 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.

[0100] 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).

[0101] 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.

[0102] 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).

[0103] The above PEBA copolymer comprises 10 to 20 polyamide blocks and 10 to 20 polyether blocks.

[0104] The above PEBA copolymer contains only one type of polyamide block and one type of polyether block.

[0105] 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.

[0106] 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.

[0107] 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.

[0108] 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).

[0109] 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.

[0110] 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.

[0111] 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.

[0112] 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.

[0113] 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.

[0114] 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.

[0115] 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.

[0116] 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).

[0117] 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).

[0118] 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.

[0119] 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.

[0120] 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.

[0121] 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).

[0122] 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.

[0123] 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®.

[0124] 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.

[0125] 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.

[0126] The above PEBA copolymer can be used in the form of a semi-solid or viscous liquid, or as a powder, pellet or granule.

[0127] In the processing aid of this disclosure, the total content of component A and the synergist 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.

[0128] 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.

[0129] 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.

[0130] In this specification, the moisture content is measured by the following method. The mass of the processing aid disclosed herein is measured before and after heating at 130°C for 24 hours, and calculated according to the following formula. Three samples are taken, and after calculating each, the average is determined and the average value is adopted. Moisture content (mass %) = [(Mass of processing aid before heating (g)) - (Mass of processing aid after heating (g))] / (Mass of processing aid before heating (g)) × 100

[0131] The method for obtaining a processing aid with a moisture content within the above range is not particularly limited. For example, a material with a low moisture content may be used, and the processing aid may be prepared under dry conditions. Alternatively, a processing aid may be prepared using ordinary materials and conditions, and then moisture may be removed by heat treatment or the like.

[0132] The processing aids of this disclosure may be obtained, for example, by a mixing step in which the materials of the processing aids are put into a mixer or the like and mixed, and a dispensing step in which the mixture is discharged from the mixer or the like. This disclosure also relates to a method for producing the above-mentioned processing aids, including the mixing step and the dispensing step.

[0133] The method of the above mixing process is not particularly limited, and may be mixing (kneading) with shear force applied, or mixing without shear force applied. Among these, kneading is preferred, and melt kneading is more preferred, in order to effectively exhibit the above-mentioned moldability. Furthermore, when melt-mixing is performed, each component may be melted during the mixing process, or it may be melted before the mixing process.

[0134] In the above manufacturing method, a molding process may be performed after the extrusion process, in which the extruded material is molded using a molding machine or the like. 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.

[0135] 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.

[0136] 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.

[0137] The processing aids of this disclosure are particularly useful as processing aids for thermoplastic resins (especially polyolefin resins).

[0138] <Masterbatch> The masterbatch of this disclosure comprises the processing aid of this disclosure and a thermoplastic resin (A). The processing aids disclosed herein may be added directly to the target material such as thermoplastic resin, but adding them in masterbatch form provides better metering stability and good dispersibility, resulting in a more effective improvement in processability.

[0139] Examples of the thermoplastic resin (A) 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.

[0140] 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.

[0141] 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 is typically 0.945 to 0.970 g / cm³. 3 Within the range of 0.945 g / cm³, 3 It has the above density.

[0142] 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).

[0143] 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 be limiting. In some embodiments, comonomers include propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, and styrene.

[0144] 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 available in concentrations of 0.900, 0.905, 0.907, and 0.910 g / cm³. 3From a low concentration to a density within the range of 0.920, 0.925, 0.930, 0.935, 0.940, or 0.945 g / cm 3 It 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 (if any) the degree of branching in the polymer produced (which is often very little). Note that LLDPE has substantially fewer long-chain branches. In certain embodiments, the polymer of the polymer composition is or comprises metallocene-catalyzed LLDPE (mLLDPE). In still other embodiments, the polymer of the polymer composition is or comprises Ziegler-Natta-catalyzed LLDPE (or ZN-LLDPE).

[0145] 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 low value such as 0.905, 0.907, 0.908, 0.910, 0.911, 0.912, 0.913, 0.914, or 0.915 g / cm 3 to any high value such as 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 within the range, and the range is from the above-mentioned low value to the high value 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 .

[0146] 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).

[0147] 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.

[0148] The thermoplastic resin (A) described above may be crystalline or non-crystalline. If the thermoplastic resin (A) is crystalline, it is preferably one with a melting point of 80 to 300°C, and more preferably one with a melting point of 100 to 200°C. If the non-crystalline thermoplastic resin (A) is non-crystalline, it is preferable that it has a processing temperature approximately the same as that of the crystalline thermoplastic resin (A) with a specified melting point range.

[0149] The thermoplastic resin (A) described above preferably has a surface free energy of 15.0 mN / m or more, more preferably 18.0 mN / m or more, more preferably 40.0 mN / m or less, and more preferably 35.0 mN / m or less.

[0150] The difference in surface free energy between the processing aid and the thermoplastic resin (A) is preferably 1.5 mN / m or more, more preferably 2.0 mN / m or more, even more preferably 4.0 mN / m or more, and particularly preferably 5.5 mN / m or more. It is also preferably 50 mN / m or less, and more preferably 45 mN / m or less. Furthermore, it is preferable that the surface free energy of the processing aid is greater than the surface free energy of the thermoplastic resin (A).

[0151] In the masterbatch of this disclosure, the mass ratio of the thermoplastic resin (A) to the processing aid (thermoplastic resin (A): processing aid) 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.

[0152] In the masterbatch of this disclosure, the total content of the thermoplastic resin (A) and the processing aid 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.

[0153] The masterbatch of this disclosure may contain components other than the thermoplastic resin (A) and the processing aid described above. Other components besides the thermoplastic resin (A) and processing aids mentioned above include, for example, anti-sticking agents; ultraviolet 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; nucleating agents and antiblocking agents such as metal salts and sorbitol acetals.

[0154] The masterbatch of this disclosure may be obtained, for example, by preparing the processing aid of this disclosure in advance and putting it into a mixer or the like with the thermoplastic resin (A), and performing a mixing step in which the mixture is mixed, and a dispensing step in which the mixture is discharged from the mixer or the like. This disclosure also relates to a method for manufacturing the masterbatch described above, which includes a mixing step and a dispensing step.

[0155] In the method for manufacturing a masterbatch according to this disclosure, a molding step may be performed after the dispensing step in which the dispensed material is molded using a molding machine or the like.

[0156] The mixing, dispensing, and molding steps in the method for producing the masterbatch of this disclosure are the same as those described in the method for producing the processing aid of this disclosure.

[0157] The masterbatch of this disclosure is particularly useful as a masterbatch for improving the processability of thermoplastic resins (especially polyolefin resins).

[0158] <Thermoplastic resin composition> The thermoplastic resin composition of this disclosure comprises the processing aid and / or the masterbatch of this disclosure and the thermoplastic resin (B). This provides good processability. In particular, good extrusion processability is obtained even during long-run molding.

[0159] The thermoplastic resin (B) can be the same as the thermoplastic resin (A), and the preferred form is also the same.

[0160] The thermoplastic resin (B) described above preferably has a surface free energy of 15.0 mN / m or more, more preferably 18.0 mN / m or more, more preferably 40.0 mN / m or less, and more preferably 35.0 mN / m or less.

[0161] The difference in surface free energy between the processing aid and the thermoplastic resin (B) is preferably 1.5 mN / m or more, more preferably 2.0 mN / m or more, even more preferably 4.0 mN / m or more, and particularly preferably 5.5 mN / m or more. It is also preferably 50 mN / m or less, and more preferably 45 mN / m or less. Furthermore, it is preferable that the surface free energy of the processing aid is greater than the surface free energy of the thermoplastic resin (B).

[0162] The thermoplastic resin composition of this disclosure may contain at least one of the processing aid and the masterbatch of this disclosure, but it is preferable to include the masterbatch of this disclosure in order to obtain better processability.

[0163] If the thermoplastic resin composition of the present disclosure includes the masterbatch of the present disclosure, the thermoplastic resin (A) and the thermoplastic resin (B) may be of the same type or of different types.

[0164] In the thermoplastic resin composition of this disclosure, the content of the processing aid is preferably 0.001% by mass or more, more preferably 0.01% by mass or more, even more preferably 0.05% by mass or more, even more preferably 0.08% by mass or more, particularly 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, particularly preferably 1.0% by mass or less.

[0165] The thermoplastic resin composition of this disclosure may contain components other than the processing aid, the masterbatch, and the thermoplastic resin (B). Other components besides the processing aid, the masterbatch, and the thermoplastic resin (B) mentioned above include, for example, anti-sticking agents; ultraviolet 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; nucleating agents such as metal salts and sorbitol acetals; and anti-blocking agents.

[0166] The thermoplastic resin composition of this disclosure may be obtained, for example, by preparing a masterbatch of this disclosure in advance and putting it into a mixer or the like with the thermoplastic resin (B) and performing a mixing step, and then discharging the mixture from the mixer or the like; or by putting the thermoplastic resin (B), the processing aid, and the thermoplastic resin (A) as needed into a mixer or the like and performing a mixing step, and then discharging the mixture from the mixer or the like. This disclosure also relates to a method for producing the above-described thermoplastic resin composition, including a mixing step and a discharging step.

[0167] In the method for producing the thermoplastic resin composition of this disclosure, a molding step may be performed after the extrusion step in which the extruded material is molded using a molding machine or the like.

[0168] The mixing step, dispensing step, and molding step in the method for producing the thermoplastic resin composition of this disclosure are the same as those described in the method for producing the processing aid of this disclosure.

[0169] <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 a 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.

[0170] The molding process described above is the same as that described in the method for manufacturing the processing aid of this disclosure.

[0171] 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 processing aid. A temperature range of 160°C to 270°C is preferable for the processing aid to exert its full effect. The molding temperature mentioned above is sometimes referred to as the extrusion temperature in the case of extrusion molding.

[0172] 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.

[0173] 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]

[0174] The present disclosure will now be further described with reference to examples, but the present disclosure is not limited to these examples.

[0175] The following materials were used in the examples and comparative examples. (Processing aid) TPU: Thermoplastic polyurethane elastomer (Shore A hardness: 97) PBAT: Polybutylene adipate terephthalate (MFR: 4g / 10min, melting point: 115℃, end molar ratio: 0.0019mol%) PBS: Polybutylene succinate (MFR: 22g / 10min, melting point: 114℃, end molar ratio: 0.0020mol%) PLA: Polylactic acid (MFR: 3g / 10min, melting point: 153℃, terminal molar ratio: 0.0018mol%) EVOH-1: Ethylene vinyl alcohol copolymer (ethylene content: 48%, MFR: 6.4, melting point: 156°C, terminal molar ratio: 0.0019 mol%) EVOH-2: Ethylene vinyl alcohol copolymer (ethylene content: 38%, MFR: 1.7, melting point: 171°C, terminal molar ratio: 0.0015 mol%) (Thermoplastic resin (B) (Matrix resin)) LLDPE-1: Metallocene-catalyzed linear low-density polyethylene (MFR: 0.7g / 10min, melting point: 123℃, MIR=28.1) (Thermoplastic resin (A) (Carrier resin)) LLDPE-2: Metalloncene-catalyzed linear low-density polyethylene (MFR: 2.0 g / 10 min, melting point: 121°C, MIR = 23.6)

[0176] <Calculation of surface free energy> (1) For washing, the sample was dissolved in an organic solvent at room temperature, then dropped into a poor solvent and the precipitate was collected. (2) From the recovered precipitate, a test specimen with a diameter of 3 cm and a thickness of 1 mm was prepared using a transfer molding machine under the conditions of a cylinder temperature of 200°C and a pressure of 300 bsr. (3) Using the prepared test specimens, contact angle measurements were performed (liquid type: water, ethylene glycol), and the surface free energy was calculated based on the Owens-Wendt method. The results are shown in Table 1. [Table 1]

[0177] Comparative Examples 1, 2, Examples 1-5 First, the carrier resin (thermoplastic resin (A)) and processing aids were melt-mixed in the proportions shown in Table 1 using a twin-screw extruder (TEX25αIII manufactured by Japan Steel Works) under the conditions of a cylinder temperature of 180-200°C, a die temperature of 200°C, and a screw rotation speed of 400 rpm to obtain a masterbatch (MB). Next, the obtained masterbatch was dry-blended with a matrix resin (thermoplastic resin (B)) at a ratio such that the concentration of processing aids in the final thermoplastic resin composition remained constant (2000 ppm), and the processability at that time was evaluated by the extrusion evaluation described below. The results are shown in Table 2. Furthermore, since the processing aid used did not contain fluorine, the fluorine content in the processing aid was 0% by mass.

[0178] <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 "-".

[0179] [Table 2]

Claims

1. The surface free energy is 29.0 to 55.0 mN / m, and it is substantially fluorine-free. A processing aid for polyolefin resins containing a structural unit represented by the following formula 1. -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-, -OC(=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-, -OC(=O)O-, or -C(OR')R'-.

2. The processing aid for polyolefin resins according to claim 1, 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).

3. The processing aid for polyolefin resins 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)-, -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).

4. The processing aid for polyolefin resins 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. A processing aid for polyolefin resins according to claim 1 or 2, wherein the melt flow rate at 190°C and a load of 2.16 kgf is 0.001 to 100 g / 10 min.

6. The processing aid for polyolefin resins according to claim 1 or 2, which is at least one selected from the group consisting of polybutylene adipate terephthalate, polybutylene succinate, polylactic acid, and ethylene vinyl alcohol copolymer.

7. A masterbatch comprising the processing aid for polyolefin resins according to claim 1 and a thermoplastic resin (A).

8. The masterbatch according to claim 7, wherein the thermoplastic resin (A) is a polyolefin resin.

9. The masterbatch according to claim 7 or 8, wherein the thermoplastic resin (A) is metallocene-catalyzed linear low-density polyethylene.

10. The masterbatch according to claim 7 or 8, wherein the difference in surface free energy between the processing aid for polyolefin resin and the thermoplastic resin (A) is 1.5 mN / m or more.

11. The masterbatch according to claim 7 or 8, wherein the difference in surface free energy between the processing aid for polyolefin resin and the thermoplastic resin (A) is 4.0 to 45 mN / m.

12. The masterbatch according to claim 7 or 8, wherein the mass ratio of the thermoplastic resin (A) and the processing aid for polyolefin resin (thermoplastic resin (A): processing aid for polyolefin resin) is 92:8 to 70:

30.

13. A processing aid for polyolefin resins according to claim 1 or 2, and / or a masterbatch according to claim 7 or 8, comprising a thermoplastic resin (B), A thermoplastic resin composition in which the thermoplastic resin (B) is a polyolefin resin.

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

15. The thermoplastic resin composition according to claim 13, wherein the difference in surface free energy between the processing aid for polyolefin resin and the thermoplastic resin (B) is 1.5 mN / m or more.

16. The thermoplastic resin composition according to claim 13, wherein the difference in surface free energy between the processing aid for polyolefin resin and the thermoplastic resin (B) is 4.0 to 45 mN / m.

17. The thermoplastic resin composition according to claim 13, wherein the content of the processing aid for polyolefin resin is 0.1 to 1.0% by mass.

18. A molded article using the thermoplastic resin composition according to claim 13.

19. The molded article according to claim 18, which is tubular, film-like, or sheet-like.

20. A method for producing a processing aid for polyolefin resins according to claim 1 or 2, comprising a mixing step and a dispensing step.

21. A method for producing a masterbatch according to claim 7 or 8, comprising a mixing step and a dispensing step.

22. A method for producing a thermoplastic resin composition according to claim 13, comprising a mixing step and a dispensing step.

23. A method for manufacturing a molded article according to claim 18, including a molding step.

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