Processing aid, master batch, thermoplastic resin composition and molded body, and method for manufacturing them

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 called melt fracture occurs in which the surface becomes rough, and good molded products cannot be obtained.

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

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0005] An object of the present disclosure is to provide a 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), which has a surface free energy of 29.0 to 55.0 mN / m.

[0008] The present disclosure (3) is a 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) (In formula 1, X represents a single bond or a divalent group which may have a functional group, Y and Z each independently represent a group consisting of at least one selected from the group consisting of a single bond, -O-, -C(=O)-, -C(=O)O-, -OC(=O)O-, -C(=NR')-, -C(=NR')O-, -OC(=NR')O-, -S-, -S(=O)-, -S(=O)O-, -OS(=O)O-, -S(=O)2-, -S(=O)2O-, -OS(=O)2O-, -P(=O)-, -P(=O)O-, -OP(=O)O-, -P(=O)2-, -P(=O)2O-, -OP(=O)2O-, -NR'-, and -C(OR')R'- (wherein R' is independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms in each occurrence); R 1 , R 2 , R 3 and R 4 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, n and m are each independently an integer of 0 to 10; At least one of X, Y, and Z is -C(=O)-, -C(=O)O-, -OC(=O)O-, or -C(OR')R'-.

[0009] The present disclosure (4) relates to a compound represented by the formula 1, in which X is 1 and X 2a divalent group composed of at least one selected from the group consisting of X 1 is a group composed of at least one selected from the group consisting of -C(=O)-, -C(=NR’)-, -S(=O)2-, -NR’-, -CR’R’-, and -C(OR’)R’- (wherein R’ is, in each occurrence, independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms). X 2 is the processing aid according to the present disclosure (3), which is an aromatic hydrocarbon group having 1 to 12 carbon atoms that may have a substituent.

[0010] The present disclosure (5) is the processing aid according to the present disclosure (4), wherein in the formula 1, X is a divalent group containing at least one selected from the group consisting of -C(=O)-, -CR’R’-, and -C(OR’)R’- (wherein R’ is, in each occurrence, independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms).

[0011] The present disclosure (6) is the processing aid according to any one of the present disclosures (3) to (5), wherein in the formula 1, Y and Z are each independently a group composed of at least one selected from the group consisting of a single bond, -O-, -C(=O)-, -C(=O)O-, -C(=NR’)-, -C(=NR’)O-, -S-, -S(=O)2-, -S(=O)2O-, -NR’-, and -C(OR’)R’- (wherein R’ is, in each occurrence, independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms).

[0012] The present disclosure (7) is the processing aid according to the present disclosure (6), wherein in the formula 1, Y and Z are each independently a group composed of at least one selected from the group consisting of a single bond, -O-, -C(=O)-, and -C(=O)O-.

[0013] The present disclosure (8) is the processing aid according to any one of the present disclosures (1) to (7), having a melt flow rate of 0.001 to 100 g / 10 minutes at 190 °C under a load of 2.16 kgf.

[0014] The present disclosure (9) is a processing aid according to any one of the present 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] The present disclosure (10) is a masterbatch containing the processing aid according to any one of the present disclosures (1) to (9) and a thermoplastic resin (A).

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

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

[0018] The present disclosure (13) is the masterbatch according to any one of the present 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 the masterbatch according to any one 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] The present disclosure (15) is the masterbatch according to any one of the present disclosures (10) to (14), wherein the mass ratio of the thermoplastic resin (A) to the processing aid (thermoplastic resin (A):processing aid) is 92:8 to 70:30.

[0021] The present disclosure (16) is a thermoplastic resin composition containing the processing aid according to any one of the present disclosures (1) to (9) and / or the masterbatch according to any one of the present disclosures (10) to (15) and a thermoplastic resin (B).

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

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

[0024] The present disclosure (19) is the 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 the 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] The present disclosure (21) is the thermoplastic resin composition according to any one of the present disclosures (16) to (20), wherein the content of the processing aid is 0.1 to 1.0% by mass.

[0027] The present disclosure (22) is a molded article using the thermoplastic resin composition according to any one of the present disclosures (16) to (21).

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

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

[0030] The present disclosure (25) is a method for producing a masterbatch according to any one of the present disclosures (10) to (15), including a mixing step and a discharging step.

[0031] The present disclosure (26) is a method for producing a thermoplastic resin composition according to any one of the present disclosures (16) to (21), including a mixing step and a discharging step.

[0032] The present disclosure (27) is a method for manufacturing a molded article as described in the present disclosure (22) or (23) including a molding step.

Effects of the Invention

[0033] According to the present disclosure, it is possible to provide a processing aid and a masterbatch that can improve the processability of a thermoplastic resin, a thermoplastic resin composition and a molded article using the same, and a method for manufacturing the same.

Modes for Carrying Out the Invention

[0034] Hereinafter, the present disclosure will be specifically described.

[0035] <Processing Aid> The processing aid of the present disclosure has a surface free energy of 28.5 mN / m or more and substantially does not contain fluorine.

[0036] According to the processing aid of the present disclosure, good processability (particularly, extrusion processability) can be obtained. The processing aid of the present disclosure has been found and completed in that the surface free energy is strongly correlated with the processability and particularly good processability can be obtained when the surface free energy is within a specific range.

[0037] The processing aid of the present disclosure preferably has a surface free energy of 28.6 mN / m or more, more preferably 29.0 mN / m or more, and preferably 55.0 mN / m or less, more preferably 50.0 mN / m or less, still more preferably 45.0 mN / m or less, still more preferably 40.0 mN / m or less, and particularly preferably 35.0 mN / m or less. The surface free energy can be calculated by the method of the examples.

[0038] The processing aid of the present disclosure is substantially free of fluorine. "Substantially free of fluorine" means that the fluorine content in the processing aid is 10 ppm or less (preferably 1 ppm or less, more preferably 0.1 ppm or less). It is particularly preferable that the processing aid of the present disclosure is free of fluorine (the fluorine content is 0 mass %).

[0039] The processing aid of the present 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 represents a single bond or a divalent group which may have a functional group, Y and Z each independently represent a group consisting of at least one selected from the group consisting of a single bond, -O-, -C(=O)-, -C(=O)O-, -OC(=O)O-, -C(=NR')-, -C(=NR')O-, -OC(=NR')O-, -S-, -S(=O)-, -S(=O)O-, -OS(=O)O-, -S(=O)2-, -S(=O)2O-, -OS(=O)2O-, -P(=O)-, -P(=O)O-, -OP(=O)O-, -P(=O)2-, -P(=O)2O-, -OP(=O)2O-, -NR'-, and -C(OR')R'- (wherein R' is independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms in each occurrence); R 1 , R 2 , R 3 and R 4 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, n and m are each independently an integer of 0 to 10; At least one of X, Y, and Z is -C(=O)-, -C(=O)O-, -OC(=O)O-, or -C(OR')R'-.

[0040] When the processing aid of the present disclosure is the above polymer, the surface free energy changes depending on the terminal mol ratio in the processing aid calculated by the following calculation method. As the terminal content increases, the surface free energy increases, and as it decreases, the surface free energy decreases. The terminal mol ratio of the processing aid of the present disclosure is preferably 0.00001 to 0.00450 mol%. Calculation method: When the polymer amount (g) is 1 g, Monomer amount (mol) = 1 g / monomer molecular weight (g / mol) Number of monomers (pieces) = monomer amount (mol) × 6.02 × 10^23 Here, when the number average molecular weight of the polymer is Mn, Number of polymer chains (pieces) = number of monomers (pieces) / Mn Number of polymer terminals (pieces) = number of polymer chains (pieces) × 2 Terminal mol number (mol) = number of polymer terminals (pieces) / 6.02 × 10^23 Terminal mol ratio (mol%) = terminal mol number (mol) / monomer amount (mol)

[0041] The terminal mol ratio changes depending on the oligomer (component with a molecular weight of 5000 g / mol or less) in the processing aid. As the oligomer amount increases, the terminal mol ratio increases, and as it decreases, the terminal mol ratio decreases. The oligomer amount can be reduced by purification methods such as recovering the precipitate generated by dropping the polymer into a poor solvent after dissolving it in a good solvent.

[0042] In the above formula 1, X is a divalent group composed of at least one selected from the group consisting of X 1 and X 2 and is a group composed of at least one selected from the group consisting of, X 1 is a group composed of at least one selected from the group consisting of -C(=O)-, -C(=NR’)-, -S(=O)2-, -NR’-, -CR’R’-, and -C(OR’)R’- (wherein R’ is, in each occurrence, independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms). X 2is preferably an aromatic hydrocarbon group having 1 to 12 carbon atoms which may have a substituent.

[0043] In the above formula 1, X is more preferably a divalent group containing at least one selected from the group consisting of -C(=O)-, -CR’R’-, and -C(OR’)R’- (wherein R’ is independently, in each occurrence, a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms).

[0044] In the above formula 1, R’ is preferably independently, in each occurrence, a hydrogen atom or a hydrocarbon group having 1 to 7 carbon atoms, more preferably a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, and still more preferably a hydrogen atom or a hydrocarbon group having 1 carbon atom.

[0045] In the above formula 1, Y and Z are each preferably independently a group composed of at least one selected from the group consisting of a single bond, -O-, -C(=O)-, -C(=O)O-, -C(=NR’)-, -C(=NR’)O-, -S-, -S(=O)2-, -S(=O)2O-, -NR’-, and -C(OR’)R’- (wherein R’ is independently, in each occurrence, a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms).

[0046] In the above formula 1, Y and Z are each preferably independently a group composed of at least one selected from the group consisting of a single bond, -O-, -C(=O)-, and -C(=O)O-.

[0047] In the above formula 1, R 1 , R 2 , R 3 and R 4 are each preferably independently a hydrogen atom or a hydrocarbon group having 1 to 7 carbon atoms, more preferably a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, and still more preferably a hydrogen atom or a hydrocarbon group having 1 carbon atom.

[0048] n and m are each independently preferably an integer of 0 to 8, more preferably an integer of 0 to 6, still more preferably an integer of 0 to 4, and particularly preferably an integer of 0 to 2.

[0049] In addition, the polymer may contain structural units other than the structural unit represented by Formula 1. Examples of the structural units that may be contained in addition to the structural unit represented by Formula 1 include glycol compounds such as ethylene glycol, propylene glycol, butanediol, heptanediol, hexanediol, octanediol, nonanediol, decanediol, 1,4-cyclohexanedimethanol, neopentyl glycol, glycerin, pentaerythritol, bisphenol A, polyethylene glycol, polypropylene glycol, and polytetramethylene glycol; dicarboxylic acids such as oxalic acid, adipic acid, sebacic acid, azelaic acid, dodecanedioic acid, malonic acid, glutaric acid, cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, naphthalenedicarboxylic acid, bis(p-carboxyphenyl)methane, anthracenedicarboxylic acid, 4,4'-diphenyletherdicarboxylic acid, 5-sodium sulfoisophthalic acid, and 5-tetrabutylphosphonium isophthalic acid; hydroxycarboxylic acids such as glycolic acid, hydroxypropionic acid, hydroxybutyric acid, hydroxyvaleric acid, hydroxycaproic acid, and hydroxybenzoic acid; lactones such as caprolactone, valerolactone, propiolactone, undecalactone, and 1,5-oxepan-2-one; and the like.

[0050] In the processing aid of the present 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, still more preferably 10% by mass or more, and particularly preferably 20% by mass or more. Further, it is preferably 99.9% by mass or less, more preferably 99% by mass or less, still more preferably 95% by mass or less.

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

[0052] The ethylene content of the ethylene-vinyl alcohol copolymer is preferably 10 mol% or more, more preferably 20 mol% or more, even more preferably 30 mol% or more, and preferably 60 mol% or less, more preferably 50 mol% or less, and even more preferably 40 mol% or less. Within the above range, the effect of improving processability is better. In this specification, the ethylene content is determined by nuclear magnetic resonance (NMR) method.

[0053] The ethylene-vinyl alcohol copolymer is preferably obtained by saponifying an ethylene-vinyl ester copolymer, and among them, the one obtained by saponifying an ethylene-vinyl acetate copolymer is particularly preferred.

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

[0055] When copolymerizing ethylene and vinyl acetate, other vinyl fatty acid esters (such as vinyl propionate and vinyl pivalate) can also be used in combination. In addition, the ethylene-vinyl alcohol copolymer can also contain 0.0002 to 0.2 mol% of a vinyl silane compound as a copolymerization component. Here, examples of the vinyl silane compound include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri(β-methoxy-ethoxy)silane, and γ-methacryloxypropylmethoxysilane. Among them, vinyltrimethoxysilane and vinyltriethoxysilane are preferably used.

[0056] When copolymerizing ethylene and vinyl acetate, monomers other than the above-mentioned vinyl fatty acid esters and vinyl silane compounds, for example, α-olefins such as propylene, isobutylene, α-octene, and α-dodecene; unsaturated acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, and itaconic acid or their anhydrides, salts, or mono- or dialkyl esters, etc.; nitriles such as acrylonitrile and methacrylonitrile; amides such as acrylamide and methacrylamide; olefin sulfonic acids such as ethylenesulfonic acid, allylsulfonic acid, and methallylsulfonic acid or their salts; alkyl vinyl ethers, vinyl ketones, N-vinylpyrrolidone, vinyl chloride, vinylidene chloride, etc. can also coexist in a small amount.

[0057] The melting point of the above processing aid is preferably 65°C or higher, more preferably 70°C or higher, still more preferably 75°C or higher, and even more preferably 80°C or higher, and is preferably 190°C or lower, more preferably 185°C or lower, still more preferably 180°C or lower. Within the above range, the effect of improving processability is better. In this specification, the melting point is the temperature corresponding to the maximum value in the melting heat curve when the temperature is raised at a rate of 10°C / min using a differential scanning calorimetry (DSC) apparatus.

[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, still more preferably 0.05 g / 10 min or more, even more preferably 0.1 g / 10 min or more, particularly preferably 0.5 g / 10 min or more, and is preferably 500 g / 10 min or less, more preferably 300 g / 10 min or less, still more preferably 150 g / 10 min or less, even more preferably 100 g / 10 min or less, even more preferably 40 g / 10 min or less, particularly preferably 20 g / 10 min or less, and most preferably 10 g / 10 min or less. Within the above range, the effect of improving processability is better. In this specification, MFR is measured under the conditions of 190 °C and a load of 2.16 kgf in accordance with ASTM D 1238.

[0059] The processing aid of the present disclosure may be a mixture of the above components (component A) and other components (component B). Examples of the other components include polyols having a melting point of 80 °C or lower, polycaprolactone, silicone, and at least one synergist selected from the group consisting of polyamide-polyether block copolymers.

[0060] The melting point of the above polyol may be 80 °C or lower, but is preferably 75 °C or lower, more preferably 70 °C or lower, still more preferably 68 °C or lower, and is preferably 10 °C or higher, more preferably 20 °C or higher, still more preferably 25 °C or higher. Within the above range, the effect of improving processability is better.

[0061] The above polyol can be represented by, for example, A[(OR 11 ) x2 OR 12 y2 wherein A is usually an alkylene having one or more ether bonds, y2 is 2 or 3, and (OR 11 ) x2 is a poly(oxyalkylene) chain having a plurality (x2) of oxyalkylene groups OR 11 , and R 11 ​is independently C2-C5 alkylene, and in some embodiments, is C2-C3 alkylene, R 12 is hydrogen, alkyl, aryl, arylalkenyl, alkylarylenyl, -C(O)-alkyl, -C(O)-aryl, -C(O)-arylalkenyl or -C(O)-alkylarylenyl, and -C(O)- is bonded to the O of OR 12 . x2 is from 10 to 230,000.

[0062] The above polyol is one in which R 11 is a homopolymer of poly(oxypropylene) where -CH2CH2- is, or R 11 is a homopolymer of poly(oxyethylene) where -C3H6- is, etc.

[0063] The above polyol is a chain having randomly distributed oxyalkylene groups (e.g., -OC2H4- and -OC3H6- units which are copolymers), or an alternating block consisting of repeating oxyalkylene groups (e.g., (-OC2H4-) a1 block and (-OC3H6-) b1 block, and the polymer containing them, and a1 + b1 is from 10 to 230,000).

[0064] In some embodiments of the above polyol, A is ethylene, -CH2-CH(-)-CH2- (derived from glycerol), CH3CH2C(CH2-)3 (derived from 1,1,1-trimethylolpropane), poly(oxypropylene), -CH2CH2-O-CH2CH2- or -CH2CH2-O-CH2CH2-O-CH2CH2-, and R 12 is hydrogen, methyl, butyl, phenyl, benzyl, acetyl, benzoyl or stearyl.

[0065] The above polyol is a dicarboxylic acid, and A[(OR 11 ) x2 OR 12 y2 ​A polyester prepared from a poly(oxyalkylene) polymer represented by A, R 11 and x2 are as defined above, and R 12 may be in the form where R is hydrogen and y2 is 2.

[0066] The above polyol may be used alone or in combination of two or more. From the viewpoint of excellent effect of improving processability, polyethylene glycol and polyethylene oxide are preferable, and polyethylene glycol is particularly preferable.

[0067] The number average molecular weight (Mn) of the above polyethylene glycol is preferably 1,000 or more, more preferably 3,000 or more, still more preferably 5,000 or more, and is preferably 50,000 or less, more preferably 45,000 or less, still more preferably 40,000 or less. Within the above range, the effect of improving processability is better. In this specification, the number average molecular weight is determined by calculation from the hydroxyl value measured in accordance with JIS K0070.

[0068] The viscosity average molecular weight (Mv) of the above polyethylene oxide is preferably 100,000 or more, more preferably 120,000 or more, still more preferably 140,000 or more, and is preferably 10,000,000 or less, more preferably 1,600,000 or less, still more preferably 500,000 or less. Within the above range, the effect of improving processability is better. In this specification, the viscosity average molecular weight is calculated as follows. Using an Ostwald viscometer, the specific viscosity ηsp of aqueous solutions with various polymer concentrations c (g / dl) in pure water is measured at 35 °C, and [η] is calculated by extrapolating the polymer concentration c to 0 based on the relationship between the reduced viscosity (ηsp / c) obtained by dividing the specific viscosity by the polymer concentration and the polymer concentration c. [η] is inserted into the following formula to calculate the viscosity average molecular weight M. Formula: [η]=6.4×10 -5 M 0.82

[0069] The above-mentioned polycaprolactone may be a homopolymer of ε-caprolactone or a modified polycaprolactone. Examples of the modified polycaprolactone include those modified by co-existing with 1,4-butanediol or the like when ring-opening polymerizing ε-caprolactone, and those modified at the terminal of the polymer with an ether, an ester group, or the like.

[0070] The weight-average molecular weight (Mw) of the above-mentioned polycaprolactone is preferably 2,000 or more, more preferably 10,000 or more, still more preferably 25,000 or more, and is preferably 100,000 or less, more preferably 95,000 or less, still more preferably 90,000 or less. Within the above range, the effect of improving processability is better. In this specification, the weight-average molecular weight is measured by polystyrene conversion by gel permeation chromatography (GPC) method.

[0071] The melting point of the above-mentioned polycaprolactone is preferably 80°C or lower, more preferably 75°C or lower, still more preferably 70°C or lower, even more preferably 68°C or lower, and is preferably 10°C or higher, more preferably 20°C or higher, still more preferably 45°C or higher. Within the above range, the effect of improving processability is better.

[0072] The above-mentioned silicone can in principle be all organosilicon compounds known to those skilled in the art by the term silicone polymer. An appropriate definition of silicone can be found in Winnacker / Kuchler: "Chemische Technik" [Chemical Technology], R. Dittmeyer, W. Keim, G. Kreysa, A. Oberholz (editors), Volume 5: "Organische Zwischenverbindungen, Polymere" [Organic Intermediates, Polymers], Chapter: "Silicones", Wiley-VCH, Weinheim, 2005.

[0073] Silicone can be a substituted or unsubstituted linear oligo- or polydiorganosiloxane, a branched silicone polymer, a silicone resin or a cross-linked silicone polymer. Of course, mixtures consisting of various silicone polymers can also be used. As already mentioned, silicone-containing copolymers, such as polyether-functional silicones, silicones containing urea or urethane units or silicone block copolymers with organic polymers, can also be used. For the purpose of better additivity, the use of high molecular weight polydiorganosiloxanes containing non-silicone components, such as fillers like particulate silicic acid, chalk, talc and sheet silicates, is particularly preferred.

[0074] Preferably, the silicone polymer corresponds to formula A, [R 13 3SiO 1 / 2 a2 [SiR 13 2O 2 / 2 b2 [R 13 SiO 3 / 2 c2 [SiO 4 / 2 d2 , where R 13 is hydrogen, -OH or an unsubstituted or substituted C1 to C18 hydrocarbon residue, and a2, b2, c2, d2 each mean 0 or an integer, and a2 + b2 + c2 + d2 is an integer from 5 to 15000.

[0075] The C1 to C18 hydrocarbon residue R 13 ​​​​Examples include alkyl residues such as methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl residues, hexyl residues such as n-hexyl residues, heptyl residues such as n-heptyl residues, octyl residues such as n-octyl residues and isooctyl residues such as 2,2,4-trimethylpentyl residues, nonyl residues such as n-nonyl residues, decyl residues such as n-decyl residues, cycloalkyl residues such as cyclopentyl residues, cyclohexyl residues, 4-ethylcyclohexyl residues and cycloheptyl residues, norbornyl residues and methylcyclohexyl residues. Among the alkyl residues, C1 to C6 residues such as methyl and ethyl residues, particularly methyl residues, are preferred.

[0076] R 13 Examples of R also include unsaturated C1 to C18 hydrocarbon residues such as alkenyl residues such as vinyl residues, 2-propen-2-yl residues, allyl residues, 3-buten-1-yl residues, 5-hexen-1-yl residues, 10-undecen-1-yl residues, and cycloalkenyl residues (2-cyclohexenyl residues, 3-cyclohexenyl residues, cyclopentadienyl residues, 2-(cyclohex-3-en-1-yl)ethyl residues); aryl residues such as phenyl residues, biphenylyl residues and naphthyl residues; alkaryl residues such as o-, m- and p-tolyl residues and phenethyl residues (2-phenylethyl residues, 1-phenylethyl residues) and aralkyl residues such as benzyl residues. Preferred unsaturated C1 to C18 hydrocarbon residues R 13 are vinyl residues and phenyl residues.

[0077] Residue R 13 Examples of substituted hydrocarbon residues as residue R include halogenated hydrocarbons such as chloromethyl residues, 3-chloropropyl residues, 3-bromopropyl residues, 3,3,3-trifluoropropyl residues and 5,5,5,4,4,3,3-heptafluoropentyl residues, and chlorophenyl residues, dichlorophenyl residues and trifluorotolyl residues.

[0078] Residue R 13 is preferably bonded to the silicone polymer represented by formula A via a Si-C bond, but can also be bonded to the silicone polymer via an oxygen atom -O-.

[0079] R 13 preferably has from 1 to 6 carbon atoms. An ethyl residue, a phenyl residue, a vinyl residue and a methyl residue 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, particularly preferably at most 7000.

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

[0082] Preferably, all residues R 13 at least 50%, more preferably at least 70%, particularly preferably at least 80% thereof mean methyl residues.

[0083] In principle, all silicone polymers corresponding to formula A can be used. However, a silicone polymer having a dynamic viscosity of more than 1000 mPa·s, preferably measured in accordance with DIN EN ISO 3219:1994 and DIN 53019, using a plate-cone system (cone CP50-2) with an opening angle of 2° and a diameter of 50 mm, a measurement temperature of 25.00 °C ± 0.05 °C and a shear rate of 1 sec-1 with Anton Paar's "MCR 302" rheometer is preferred.

[0084] Among silicones, silicone polymers having a very high molecular weight, for example, UHMW polysiloxanes (ultra-high molecular weight; described in K.J. Ryan et al., Journal of Vinyl & Additive Technology, March 2000, Vol. 6, No. 1, pages 7 to 19) may be used.

[0085] 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.

[0086] A 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 rotational rheometer according to DIN EN ISO 3219:1994 and DIN 53019, where a plate-plate system (diameter 25 mm) with a measurement gap of 0.5 mm is used. The measurement temperature is 25.00 °C + / - 0.1 °C. The shear rate gradient is 0.1 sec -1 -1. The viscosity description represents the arithmetic mean value of three individual measurements performed independently.

[0087] Due to being inexpensive and effective, among the above UHMW polysiloxanes, high molecular weight polydimethylsiloxanes having a dynamic viscosity between 1 kPa·s and 50 kPa·s, preferably between 10 and 40 kPa·s, particularly preferably between 15 and 30 kPa·s (preferably measured by the above method) are particularly preferred.

[0088] The above-mentioned UHMW polysiloxane includes commercially available UHMW polysiloxanes such as MULTIBASE® MB50-001 and MULTIBASE® MB50-002 manufactured by Dupont, GENIOPLAST® PELLET S, GENIOPLAST® PELLET P PlUS, GENIOPLAST® PE50S08, and GENIOPLAST® PP50S12 manufactured by Asahi Kasei Wacker Silicone, and mixtures thereof. Among them, MB50-002 and GENIOPLAST® PELLET S are preferred.

[0089] The silicone polymer is commercially available in the form of pellets / granules or masterbatches and can be used immediately, for example, it can be mixed with thermoplastic plastic granules before these further processes.

[0090] The above-mentioned polyamide-polyether block copolymer is a copolymer having a polyamide block and a polyether block in the polymer backbone. In the present disclosure, such a block copolymer having a polyamide block and a polyether block can also be referred to as a "polyamide / polyether block copolymer". Further, it can be abbreviated as "PEBA copolymer" or "PEBA". In some embodiments of the present disclosure, the PEBA copolymer can be represented by the following general formula. [Chemical formula]

[0091] Here, PA represents a polyamide block, PE represents a polyether block, p represents the length of the PEBA copolymer, and represents the total number of polyamide and polyether blocks. In some embodiments of the present disclosure, the PEBA copolymer can be represented by the following general formula. [Chemical formula]

[0092] Here, EG is a first unspecified end group, B is an unspecified crosslinking group, and EG * is a second unspecified end group, and EG, B, and EG * are determined by the synthesis method used to produce the PEBA copolymer. Here, n2 represents the length of the polyamide block, x3 represents the length of the amide component within the polyamide block, m1 represents the length of the poly(ether) block, y3 represents the length of the ether component within the poly(ether) block, p represents the length of the PEBA copolymer, and indicates the total number of polyamide and polyether blocks. In some embodiments of the present disclosure, the PEBA copolymer can be represented by the following general formula.

Chemical formula

[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 indicates the total number of polyamide and polyether blocks.

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

[0096] In an embodiment, the number average molecular weight Mn of the polyamide block in the PEBA copolymer is from about 100 to about 15,000 g / mol, or from about 300 to about 15,000 g / mol, or from about 600 to about 10,000 g / mol, or from about 600 to about 5,000 g / mol. The number average molecular weight Mn of the polyether block in the above PEBA copolymer is from about 100 to about 15,000 g / mol, from about 100 to about 10,000 g / mol, from about 100 to about 6,000 g / mol, from about 100 to about 3,000 g / mol, from about 200 to about 6,000 g / mol, from about 200 to about 3,000 g / mol, from about 250 to about 2,000 g / mol, from about 750 to about 3,500 g / mol, or from about 1,000 to about 3,000 g / mol.

[0097] The number average molecular weight Mn of the above PEBA copolymer is from 10,000 to 500,000 g / mol, including sub-ranges within this range and any numbers within this range. For example, in an embodiment of the present disclosure, the number average molecular weight Mn of the PEBA copolymer is from 10,000 to 400,000 g / mol, or from 10,000 to 300,000 g / mol, from 10,000 to 250,000 g / mol, or from 15,000 to 300,000 g / mol, or from 20,000 to 300,000 g / mol, or from 15,000 to 200,000 g / mol, or from 20,000 to 200,000 g / mol, or from 30,000 to 250,000 g / mol, or from about 25,000 to about 75,000 g / mol, or from about 50,000 to about 75,000 g / mol, or from about 100,000 to about 150,000 g / mol. The number average molecular weight Mn of the above PEBA copolymer is at least 10,000 g / mol, at least 20,000 g / mol, at least 25,000 g / mol, exceeding 25,000 g / mol, at least 30,000 g / mol, exceeding 30,000 g / mol, at least 35,000 g / mol, exceeding 35,000 g / mol, at least 50,000 g / mol, or exceeding 50,000 g / mol.

[0098] In an embodiment, the weight average molecular weight Mw of the PEBA copolymer is from 25,000 to 500,000 g / mol, including sub-ranges within this range and any numbers within this range. For example, in embodiments of the present disclosure, the weight average molecular weight Mw of the PEBA copolymer is from about 100,000 to about 250,000 g / mol, or from about 100,000 to about 150,000 g / mol, or from about 125,000 to about 150,000 g / mol. The polyamide and polyether blocks within the above PEBA copolymer can be randomly distributed.

[0099] The above PEBA copolymer includes a polyamide block and a polyether block, and the polyamide block may account for at least 50% by mass of the copolymer. The above PEBA copolymer includes a polyamide block and a polyether block, and the polyether block may account for at least 50% by mass of the copolymer. Further, the PEBA copolymer includes a polyamide block and a polyether block, and the molar ratio of the polyamide block to the polyether block may be in the range of 1:3 to 3:1, or 1:2 to 2:1, or 3:2 to 1:3, or 2:3 to 3:1, or about 1:1.

[0100] By reacting the above polyamide and polyether block precursors, a PEBA copolymer having a polyamide block and a polyether block can be prepared. For example, lactam, polyether diol, and a chain-limiting diacid are reacted together in the presence of a small amount of water to obtain a PEBA copolymer having polyamide blocks and polyether blocks with variable lengths and a statistically random distribution within the block copolymer chains. The above polyether block is derived from poly(oxyethylene), poly(oxypropylene), or poly(tetramethylene ether) glycol, and each may be co-condensed with a polyamide block containing carboxylic acid chain ends in its natural state. A chain limiter is also present during the polycondensation reaction to give a PEBA copolymer containing polyamide blocks and polyether blocks randomly distributed within the block copolymer. The above polyether block is derived from poly(oxyethylene), poly(oxypropylene), or poly(tetramethylene ether) glycol, which are first converted to polyether diamines by amination and then co-condensed with a polyamide block containing carboxylic acid chain ends. A chain limiter is also present during the polycondensation reaction to give a PEBA copolymer containing polyamide blocks and polyether blocks randomly distributed within the block copolymer. The above polyether block can be derived from poly(oxyethylene), also known as polyethylene glycol (PEG). The above polyether block can be derived from poly(oxypropylene), also known as polypropylene glycol (PPG). The above polyether block can be derived from poly(tetramethylene ether) glycol (PTMG), also known as polytetramethylene oxide (PTMEO) or polytetrahydrofuran (PTHF).

[0101] The above PEBA copolymer contains 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 above-mentioned PEBA copolymer contains: 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 contains: i) a polyamide block which is polyamide-12 (PA-12); and ii) a polyether block which is polyethylene glycol (PEG).

[0103] The above-mentioned PEBA copolymer contains 10 to 20 polyamide blocks and 10 to 20 polyether blocks.

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

[0105] The above-mentioned PEBA copolymer contains: i) a polyamide block which is polyamide-12 (PA-12); and ii) a polyether block which is polyethylene glycol (PEG), wherein the polyamide-12 block accounts for about 30% to 70% by mass of the copolymer, and the polyethylene glycol block accounts for about 70% to 30% by mass of the copolymer.

[0106] The above-mentioned PEBA copolymer contains: i) a polyamide block which is polyamide-12 (PA-12); and ii) a polyether block which is polyethylene glycol (PEG), wherein the polyamide-12 block accounts for about 40% to 60% by mass of the copolymer, and the polyethylene glycol block accounts for about 60% to 40% by mass of the copolymer.

[0107] The above-mentioned PEBA copolymer contains: i) a polyamide block which is polyamide-12 (PA-12) and ii) a polyether block which is polyethylene glycol (PEG), wherein the polyamide-12 block represents about 45% by mass of the copolymer, and the polyethylene glycol block represents about 55% by mass of the copolymer.

[0108] The above-mentioned PEBA copolymer contains i) 10 to 20 polyamide blocks that are polyamide-12 (PA-12), and ii) 10 to 20 polyether blocks that are polyethylene glycol (PEG).

[0109] The above-mentioned PEBA copolymer contains i) a polyamide block that is polyamide-12 (PA-12), and ii) a polyether block that is polyethylene glycol (PEG), and has a number average molecular weight Mn of about 25,000 to about 75,000 g / mol.

[0110] The above-mentioned PEBA copolymer contains i) a polyamide block that is polyamide-12 (PA-12), and ii) a polyether block that is polyethylene glycol (PEG), and has a number average molecular weight Mn of about 50,000 to about 75,000 g / mol. The above-mentioned PEBA copolymer contains i) a polyamide block that is polyamide-12 (PA-12) and ii) a polyether block that is polyethylene glycol (PEG), and has a number average molecular weight Mn of about 66,100 g / mol.

[0111] The above-mentioned PEBA copolymer contains i) a polyamide block that is polyamide-12 (PA-12), and ii) a polyether block that is polyethylene glycol (PEG), and has a weight average molecular weight Mw of about 100,000 to about 150,000 g / mol.

[0112] The above-mentioned PEBA copolymer contains i) a polyamide block that is polyamide-12 (PA-12), and ii) a polyether block that is polyethylene glycol (PEG), and has a weight average molecular weight Mw of about 125,000 to about 150,000 g / mol.

[0113] The above-mentioned PEBA copolymer contains i) a polyamide block that is polyamide-12 (PA-12) and ii) a polyether block that is polyethylene glycol (PEG), and has a weight average molecular weight Mw of about 134,000 g / mol.

[0114] In one embodiment of the present disclosure, the PEBA copolymer includes i) a polyamide block that is polyamide-6 (PA-6), and ii) a polyether block that is polyethylene glycol (PEG). The above PEBA copolymer includes i) a polyamide block that is polyamide-6 (PA-6) and ii) a polyether block that is polyethylene glycol (PEG), where the polyamide-6 block represents from about 30% to 60% by mass of the copolymer, and the polyethylene glycol block represents from about 70% to 40% by mass of the copolymer.

[0115] The above PEBA copolymer includes i) a polyamide block that is polyamide-6 (PA-6) and ii) a polyether block that is polyethylene glycol (PEG), where the polyamide-6 block represents from about 50% to 35% by mass of the copolymer, and the polyethylene glycol block represents from about 50% to 65% by mass of the copolymer.

[0116] The above PEBA copolymer includes i) from 10 to 20 polyamide blocks that are polyamide-6 (PA-6), and ii) from 10 to 20 polyether blocks that are polyethylene glycol (PEG).

[0117] The above PEBA copolymer includes i) a polyamide block that is polyamide-11 (PA-11), and ii) a polyether block that is polyethylene glycol (PEG). In one embodiment of the present disclosure, the PEBA copolymer includes i) a polyamide block that is polyamide-12 (PA-12), and ii) a polyether block that is polytetrahydrofuran (PTHF).

[0118] The above-mentioned PEBA copolymer contains i) a polyamide block that is polyamide-12 (PA-12), and ii) a polyether block that is polytetrahydrofuran (PTHF), where the polyamide-12 block represents from about 75% to 10% by mass of the copolymer, and the polytetrahydrofuran block represents from about 25% to 90% by mass of the copolymer.

[0119] The above-mentioned PEBA copolymer contains i) a polyamide block that is polyamide-12 (PA-12), and ii) a polyether block that is polytetrahydrofuran (PTHF), where the polyamide-12 block represents from about 80% to 60% by mass of the copolymer, and the polytetrahydrofuran block represents from about 20% to 40% by mass of the copolymer.

[0120] The above-mentioned PEBA copolymer contains i) a polyamide block that is polyamide-12 (PA-12), and ii) a polyether block that is polytetrahydrofuran (PTHF), where the polyamide-12 block represents from about 40% to 60% by mass of the copolymer, and the polytetrahydrofuran block represents from about 60% to 40% by mass of the copolymer.

[0121] The above-mentioned PEBA copolymer contains i) a polyamide block that is polyamide-12 (PA-12), and ii) a polyether block that is polytetrahydrofuran (PTHF), where the polyamide-12 block represents from about 30% to 10% by mass of the copolymer, and the polytetrahydrofuran block represents from about 70% to 90% by mass of the copolymer. The above-mentioned PEBA copolymer contains i) 10 to 20 polyamide blocks that are polyamide-12 (PA-12), and ii) 10 to 20 polyether blocks that are polytetrahydrofuran (PTHF).

[0122] The above-mentioned PEBA copolymer contains i) a polyamide block which is polyamide-12 (PA-12) and ii) a polyether block which is polytetrahydrofuran (PTHF), and has a number-average molecular weight Mn of from about 25,000 to about 75,000 g / mol. The above-mentioned PEBA copolymer contains i) a polyamide block which is polyamide-12 (PA-12) and ii) a polyether block which is polytetrahydrofuran (PTHF), and has a number-average molecular weight Mn of from about 40,000 to about 60,000 g / mol. In an embodiment of the present disclosure, the PEBA copolymer contains i) a polyamide block which is polyamide-12 (PA-12) and ii) a polyether block which is polytetrahydrofuran (PTHF), and has a number-average molecular weight Mn of about 50,000 g / mol.

[0123] The above-mentioned PEBA copolymer contains i) a polyamide block which is polyamide-6 (PA-6) and ii) a polyether block which is polytetrahydrofuran (PTHF). The above-mentioned PEBA copolymer contains i) a polyamide block which is polyamide-11 (PA-11) and ii) a polyether block which is polytetrahydrofuran (PTHF). The above-mentioned PEBA copolymer is a commercially available elastomer and is sold under the trade name PEBAX®.

[0124] The above-mentioned PEBA copolymer is a commercially available elastomer selected from the group consisting of: PEBAX 2533 SA 01, PEBAX 2533 SA 01 MED, PEBAX 2533 SD 02, PEBAX 3533 SA 01, PEBAX 3533 SA 01 MED, PEBAX 3533 SP01, PEBAX 4011, PEBAX 4033 SA 01, PEBAX 4033 SA 01 MED, PEBAX 4033 SP01, PEBAX 4533 SA 01, PEBAX 4533 SA 01 MED, PEBAX 4533 SP01, PEBAX 5513 SA 01, PEBAX 5513 SP01, PEBAX 5533 SA 01, PEBAX 5533 SA 01 MED, PEBAX 5533 SN 70 BLACK, PEBAX 5533 SP01, PEBAX SA 01, PEBAX 6333 SA 01 MED, PEBAX SP01, PEBAX 6333 SP01, PEBAX 6333 SA 01, PEBAX, PEBAX 3533 SA 01, PEBAX 3533 SA 01 MED, PEBAX 3533 SP01, PEBAX 4011 SA 01, PEBAX 4033 SA 01 MED, PEBAX 4033 SP01, PEBAX 4033 SA 01 MED, PEBAX Clear 2533, PEBAX ES 2533 UV, PEBAX MH 2533, PEBAX MH2030, PEBAX MV 5513 SA 01, PEBAX MV 5513 SA 01 MED, PEBAX MV 5533 SP01, PEBAX MV 5533, PEBAX MV 5533 SP01, PEBAX RNEW® 30R51 SA 01, PEBAX RNEW 35R53 SP01, PEBAX RNEW 70R53 SP01, PEBAX RNEW 55R53 SP01, PEBAX RNEW 63R53 SP01, PEBAX RNEW 70R53 SP01, PEBAX RNEW 70R53 SP01, PEBAX, PEBAX RNEW 72R53 SP01, PEBAX RNEW 80R53 SP 02 and mixtures thereof. The above-mentioned PEBA copolymer is a commercially available elastomer and is sold under the trade names VESTAMID® or VESTAMID E.

[0125] The above-mentioned PEBA copolymer is a commercially available elastomer selected from the group consisting of VESTAMID D, VESTAMID DX, VESTAMID E, VESTAMID EX, VESTAMID Care, VESTAMID Care ML, VESTAMID Care ME, VESTAMID Care ME-B, VESTAMID L, VESTAMID LX, VESTAMID NRG, VESTAMID Terra, VESTAMID X, and mixtures thereof. Among them, Pebax MV1072 is preferred.

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

[0127] In the processing aid of the present disclosure, the total content of the above-mentioned component A and the above-mentioned synergist is preferably 80% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass or more, and particularly preferably 100% by mass.

[0128] Other components may include, for example, anti-sticking agents; ultraviolet absorbers; flame retardants; reinforcing materials such as glass fibers and glass powders; stabilizers such as minerals and flakes; lubricants such as silicone oil and molybdenum disulfide; pigments such as titanium dioxide and valve handles; conductive agents such as carbon black; impact resistance improvers such as rubber; antioxidants such as hindered phenols and phosphorus-based; nucleating agents such as metal salts and acetals of sorbitol, and anti-blocking agents can also be used.

[0129] The water content of the processing aid of the present disclosure is preferably 1.0% by mass or less, more preferably 0.5% by mass or less, still more preferably 0.2% by mass or less, and most preferably 0.1% by mass or less. The lower limit is not particularly limited and may be 0% by mass.

[0130] In this specification, the water content is measured by the following method. Measure the mass of the processing aid of the present disclosure before and after heating at 130°C for 24 hours, and calculate according to the following formula. Take the sample three times, calculate each time, then obtain the average, and adopt the average value. Water content (mass %) = [(mass of the processing aid before heating (g)) - (mass of the processing aid after heating (g))] / (mass of the processing aid before heating (g)) × 100

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

[0132] The processing aid of the present disclosure may be obtained, for example, by performing a mixing step of charging the materials of the above processing aid into a mixer or the like and mixing them, and a discharging step of discharging the mixture from the mixer or the like. The present disclosure is also a method for manufacturing the above processing aid including the mixing step and the discharging step.

[0133] The method of the above mixing step is not particularly limited, and it may be mixing (kneading) with shear force applied, or mixing without shear force applied. Among them, in order to effectively exhibit the above moldability, kneading is preferable, and melt kneading is more preferable. Also, when performing melt kneading, each component may be melted in the mixing step, or may be melted before the mixing step.

[0134] In the above manufacturing method, after the discharging step, a molding step of molding the discharged material with a molding machine or the like may be performed. The method of the above molding step is not particularly limited, and examples include extrusion molding, injection molding, blow molding, etc. Among them, in order to effectively exhibit the above moldability, extrusion molding is preferable.

[0135] For the above extrusion molding, an extruder is used. Examples of the extruder include a single-screw extruder, a twin-screw extruder, a tandem extruder, etc. The extruder generally includes a cylinder, a screw housed in the cylinder, a die attached to the tip of the cylinder, and a hopper for supplying pellets to the cylinder.

[0136] The various conditions related to the above molding are not particularly limited and can be appropriately set according to the composition and amount of the composition, the shape and size of the desired molded product, etc.

[0137] The processing aid of the present disclosure is particularly useful as a processing aid for thermoplastic resins (especially polyolefin resins).

[0138] <Masterbatch> The masterbatch of the present disclosure contains the processing aid of the present disclosure and a thermoplastic resin (A). The processing aid of the present disclosure may be added directly to an object such as a thermoplastic resin, but adding it in the form of a masterbatch can obtain better metering stability and good dispersibility, and thus the effect of improving processability is better.

[0139] Examples of the above 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, polyvinyl chloride (PVC), etc. These may be used alone or in combination of two or more. From the viewpoint of better improving the processability, polyolefin polymers (polyolefin resins) are preferred.

[0140] Among polyolefin polymers, for example, homopolymers (e.g., homopolymers of C2-C10 α-olefins, preferably C2-C6 α-olefins) can be mentioned. 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 less than 0.945 g / cm 3 and often less than 0.935 g / cm 3 and, for example, in the range from 0.900, 0.905, or 0.910 g / cm 3 to 0.920, 0.925, 0.927, 0.930, 0.935, or 0.945 g / cm 3 . Unless otherwise specified herein, all polymer density values are determined in accordance with ASTM D1505. The sample is molded under ASTM D4703-10a, Procedure C and allowed to stand for 40 hours under ASTM D618-08 (23 ± 2 °C and relative humidity 50 ± 10%) prior to 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 the polymerization art and will not be discussed further herein. When more highly linear ethylene homopolymers are produced (e.g., using gas phase or slurry phase polymerization with any of the above catalysts), it is called HDPE (high density polyethylene) and typically has a density of 0.945 g / cm or more, such as in the range from 0.945 to 0.970 g / cm 3 and has a density of 0.945 g / cm 3 or more.

[0142] Furthermore, examples of polymers include copolymers of two or more C2-C40 α-olefins, such as C2-C20 α-olefins, such as ethylene-α-olefin copolymers, or propylene-α-olefin copolymers (for example, propylene-ethylene copolymers or propylene-ethylene-diene terpolymers (sometimes known as EPDM or PEDM)). Specific examples contemplated herein include copolymers of ethylene and one or more C3-C20 α-olefin comonomers (1-butene, 1-hexene, 1-octene, or mixtures of two or more thereof being preferred in various embodiments), such as C4-C12 α-olefin comonomers. Ethylene copolymers (for example, copolymers of ethylene and one or more C3-C20 α-olefins) can contain at least 90, 94, 95, or 96 wt% (for example, in a range from low values of 80, 85, 90, 80, 85, 93, 93, 95, 96, or 97 wt% to high values of 94, 95, 95.5, 91, 92, 97, 94, 97.5, or 98 wt%), and can contain at least 96 wt%, or 96.5 wt% of ethylene-derived units, based on the total amount of ethylene-derived units and comonomer-derived units, and can include a range from any of the low values to any of the high values described above. For example, an ethylene copolymer can contain 94 or 95 wt% to 97 or 98 wt% of ethylene-derived units, based on the total amount of ethylene-derived units and comonomer-derived units. The balance of the copolymer (based on ethylene-derived units and comonomer-derived units) consists of comonomer-derived units. For example, comonomer units (for example, units derived from C2-C20 α-olefins such as units derived from butene, hexene, and / or octene) can be present in the ethylene copolymer in amounts from low values of 2, 2.5, 3, 3.5, 4, 4.5, 5, or 6 wt% to high values of 3, 4, 5, 6, 7, 8, 9, 10, 15, or 20 wt%, and the range is from the low value to the intended high value described above (provided the high value is greater than the low value).

[0143] For ethylene-based, propylene-based, or other α-olefin-based copolymers, several suitable comonomers are already known, but in various embodiments, other α-olefin comonomers are contemplated. For example, the α-olefin comonomer may be linear or branched, and two or more comonomers can be used if desired. Examples of suitable comonomers include linear C3-C20 α-olefins (such as butene, hexene, octene as already mentioned), and α-olefins having one or more C1-C3 alkyl branches or aryl groups. For example, propylene; 3-methyl-1-butene; 3, 3-dimethyl-1-butene; 1-pentene; 1-pentene having one or more methyl, ethyl or propyl substituents; 1-hexene having one or more methyl, ethyl or propyl substituents; 1-heptene having one or more methyl, ethyl or propyl substituents; 1-octene having one or more methyl, ethyl or propyl substituents; 1-nonene having one or more methyl, ethyl or propyl substituents; ethyl, methyl or dimethyl substituted 1-decene; 1-dodecene; styrene. The above list of comonomers is merely illustrative and not intended to be limiting. In some embodiments, the comonomer includes propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene and styrene.

[0144] In certain embodiments, the polymer can include an ethylene copolymer or can be an ethylene copolymer (in accordance with those described above). The ethylene copolymer can be produced by gas, slurry or solution phase polymerization, and some particularly preferred ethylene copolymers can be produced by gas or slurry phase polymerization. Specific examples are linear low density polyethylene (LLDPE), a copolymer of ethylene and one or more α-olefins, and is polymerized in the presence of one or more single-site catalysts such as one or more Ziegler-Natta catalysts, one or more metallocene catalysts, and combinations thereof. Such LLDPE has a density of 0.900, 0.905, 0.907, 0.910 g / cm 3from a low concentration 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 of 3 . 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 includes metallocene-catalyzed LLDPE (mLLDPE). In still other embodiments, the polymer of the polymer composition is or includes Ziegler-Natta-catalyzed LLDPE (or ZN-LLDPE).

[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 as intended herein (for example, 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 (such as 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 affect the processing aid composition for molding the molded article. Generally, the PPA composition is preferably used in a polymer having a melt index (MI or I2, measured at 190 °C under a load of 2.16 kg according to ASTM D1238) 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, etc., and 1.5 g / 2.0 min or less, preferably 2.5 g / 3.0 min or less. The melt index ratio (MIR) (MIR is defined herein as the ratio of the high load melt index (HLMI) (measured according to ASTM D1238 at 190 °C under a load of 21.6 kg) to the melt index, or HLMI / MI) can generally have an MIR in the range of 10, 12, or 15 to 19, 20, 21, 22, 25, 27, 30, 35, 40, 45, 50, 60, 65, 70, 75, 80, 85, 90, 95, or 100 in the polymers of some embodiments. Optionally, the MI in such polymers can be less than 1.5 g / 10 min, such as less than 1.0 g / 10 min (e.g., from 0.1, 0.2, or 0.5 g / 10 min to 1.0; or any of 1.1, 1.2, 1.3, 1.4, or less than 1.5 g / 10 min).

[0147] Also, the above LLDPE is preferably at least one selected from the group consisting of Ziegler-Natta catalyst type LLDPE and metallocene catalyst type LLDPE. Particularly, metallocene catalyst type LLDPE is preferred.

[0148] The above thermoplastic resin (A) may or may not have crystallinity. When the above thermoplastic resin (A) has crystallinity, those having a melting point of 80 to 300 °C are preferred, and those having a melting point of 100 to 200 °C are more preferred. The non-crystalline thermoplastic resin (A) preferably has a processing temperature substantially equivalent to that of the crystalline thermoplastic resin (A) whose melting point range is indicated.

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

[0150] The difference in surface free energy between the above-mentioned processing aid and the above-mentioned thermoplastic resin (A) is preferably 1.5 mN / m or more, more preferably 2.0 mN / m or more, still more preferably 4.0 mN / m or more, and particularly preferably 5.5 mN / m or more. Also, it is preferably 50 mN / m or less, more preferably 45 mN / m or less. Moreover, it is preferable that the surface free energy of the above-mentioned processing aid > the surface free energy of the above-mentioned thermoplastic resin (A).

[0151] In the masterbatch of the present disclosure, the mass ratio of the above-mentioned thermoplastic resin (A) and the above-mentioned processing aid (thermoplastic resin (A): processing aid) is preferably 99:1 to 1:99. The above mass ratio is more preferably 97:3 to 50:50, still more preferably 95:5 to 60:40, and particularly preferably 92:8 to 70:30.

[0152] In the masterbatch of the present disclosure, the total content of the above-mentioned thermoplastic resin (A) and the above-mentioned processing aid is preferably 80% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass or more, and particularly preferably 100% by mass.

[0153] The masterbatch of the present disclosure may contain components other than the above-mentioned thermoplastic resin (A) and the above-mentioned processing aid. As components other than the above-mentioned thermoplastic resin (A) and the above-mentioned processing aid, for example, an anti-blocking agent; an ultraviolet absorber; a flame retardant; a reinforcing material such as glass fiber and glass powder; a stabilizer such as mineral and flake; a lubricant such as silicone oil and molybdenum disulfide; a pigment such as titanium dioxide and valve handle; a conductive agent such as carbon black; an impact resistance improver such as rubber; an antioxidant such as hindered phenol type and phosphorus type; a nucleating agent such as metal salt and acetal of sorbitol, and an anti-blocking agent can be used.

[0154] The masterbatch of the present disclosure may be obtained, for example, by previously preparing the processing aid of the present disclosure, charging it into the above-mentioned thermoplastic resin (A) together with a mixer or the like, and performing a mixing step of mixing, and a discharging step of discharging the mixture from a mixer or the like. The present disclosure is also a method for producing the above-mentioned masterbatch including the mixing step and the discharging step.

[0155] In the method for producing the masterbatch of the present disclosure, after the discharging step, a molding step of molding the discharged product with a molding machine or the like may be performed.

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

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

[0158] <Thermoplastic resin composition> The thermoplastic resin composition of the present disclosure includes the processing aid of the present disclosure and / or the masterbatch of the present disclosure, and a thermoplastic resin (B). Thereby, good processability can be obtained. In particular, good extrusion processability can be obtained even during long-run molding.

[0159] As the above-mentioned thermoplastic resin (B), the same ones as the above-mentioned thermoplastic resin (A) can be used, and the preferred forms are also the same.

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

[0161] The difference in surface free energy between the above-mentioned processing aid and the above-mentioned thermoplastic resin (B) is preferably 1.5 mN / m or more, more preferably 2.0 mN / m or more, still more preferably 4.0 mN / m or more, and particularly preferably 5.5 mN / m or more. Also, it is preferably 50 mN / m or less, more preferably 45 mN / m or less. Moreover, it is preferable that the surface free energy of the above-mentioned processing aid > the surface free energy of the above-mentioned thermoplastic resin (B).

[0162] The thermoplastic resin composition of the present disclosure only needs to contain at least one of the processing aid of the present disclosure and the masterbatch of the present disclosure. However, from the viewpoint of obtaining better processability, it is preferable to contain the masterbatch of the present disclosure.

[0163] When the thermoplastic resin composition of the present disclosure contains the masterbatch of the present disclosure, the above-mentioned thermoplastic resin (A) and the above-mentioned thermoplastic resin (B) may be of the same type or different types.

[0164] In the thermoplastic resin composition of the present disclosure, the content of the above-mentioned processing aid is preferably 0.001% by mass or more, more preferably 0.01% by mass or more, still more preferably 0.05% by mass or more, even more preferably 0.08% by mass or more, and particularly preferably 0.1% by mass or more. Also, it is preferably 5% by mass or less, more preferably 3% by mass or less, still more preferably 2% by mass or less, and particularly preferably 1.0% by mass or less.

[0165] The thermoplastic resin composition of the present disclosure may contain components other than the above-mentioned processing aid, the above-mentioned masterbatch, and the above-mentioned thermoplastic resin (B). Examples of components other than the above processing aid, the above masterbatch, and the above thermoplastic resin (B) include anti-blocking 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 valve handles; conductive agents such as carbon black; impact resistance improvers such as rubber; antioxidants such as hindered phenols and phosphorus-based compounds; nucleating agents such as metal salts and acetals of sorbitol; and anti-blocking agents can be used.

[0166] The thermoplastic resin composition of the present disclosure may be obtained, for example, by previously preparing the masterbatch of the present disclosure, charging it into a mixer or the like together with the above thermoplastic resin (B), and performing a mixing step of mixing, and a discharging step of discharging the mixture from the mixer or the like. Alternatively, it may be obtained by charging the above thermoplastic resin (B), the above processing aid, and, if necessary, the above thermoplastic resin (A) into a mixer or the like and performing a mixing step of mixing, and a discharging step of discharging the mixture from the mixer or the like. The present disclosure is also a method for producing the above thermoplastic resin composition including a mixing step and a discharging step.

[0167] In the method for producing the thermoplastic resin composition of the present disclosure, after the discharging step, a molding step of molding the discharged material with a molding machine or the like may be performed.

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

[0169] <Molded article> The molded article of the present disclosure is made of the thermoplastic resin composition of the present disclosure, and may be obtained, for example, by performing a molding step of molding the thermoplastic resin composition of the present disclosure. The present disclosure is also a method for producing the molded article of the present disclosure including a molding step. Note that the thermoplastic resin composition of the present disclosure is suitable for molded articles in the form of tubes, films, or sheets, but is also applicable to molded articles of other shapes.

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

[0171] In the above-mentioned molding process, the molding temperature (extrusion temperature) during molding is generally carried out at a temperature equal to or higher than the melting point of the above-mentioned thermoplastic resin (B) and lower than the decomposition temperature of the above-mentioned processing aid. In terms of the significant exertion of the effect of the above-mentioned processing aid, it is preferably in the range of 160°C or higher and 270°C or lower. In the case of the above-mentioned molding temperature, in the case of extrusion molding, it may be referred to as the extrusion temperature.

[0172] The use of the molded body of the present disclosure is not particularly limited, and examples include tableware such as bags, coating materials, beverage containers, wires, cables, pipes, fibers, bottles, gasoline tanks, and other various industrial molded products.

[0173] Although the embodiments have been described above, it will be understood that various changes in form and details are possible without departing from the spirit and scope of the claims.

Examples

[0174] Next, the present disclosure will be described in more detail with reference to examples, but the present disclosure is not limited only to these examples.

[0175] In the examples and comparative examples, the following materials were used. (Processing aid) TPU: Thermoplastic polyurethane elastomer (Shore A hardness: 97) PBAT: Polybutylene adipate terephthalate (MFR: 4 g / 10 min, melting point: 115°C, terminal mol ratio: 0.0019 mol%) PBS: Polybutylene succinate (MFR: 22 g / 10 min, melting point: 114°C, terminal mol ratio: 0.0020 mol%) PLA: Polylactic acid (MFR: 3 g / 10 min, melting point: 153°C, terminal mol ratio: 0.0018 mol%) EVOH-1: Ethylene vinyl alcohol copolymer (ethylene content: 48%, MFR: 6.4, melting point: 156 °C, terminal mol ratio: 0.0019 mol%) EVOH-2: Ethylene vinyl alcohol copolymer (ethylene content: 38%, MFR: 1.7, melting point: 171 °C, terminal mol ratio: 0.0015 mol%) (Thermoplastic resin (B) (matrix resin)) LLDPE-1: Metallocene-catalyzed linear low-density polyethylene (MFR: 0.7 g / 10 min, melting point: 123 °C, MIR = 28.1) (Thermoplastic resin (A) (carrier resin)) LLDPE-2: Metallocene-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 cleaning, the measurement sample was dissolved in an organic solvent at room temperature, then dropped into a poor solvent, and the precipitate was collected. (2) From the collected precipitate, using a transfer molding machine, a test piece with a diameter of 3 cm × thickness of 1 mm was prepared under the conditions of a cylinder temperature of 200 °C and a pressure of 300 bsr. (3) Using the prepared test piece, contact angle measurement (liquid types: water, ethylene glycol) was performed, and the surface free energy was calculated based on the formula of the Owens-Wendt method. The results are shown in Table 1.

Table 1

[0177] Comparative Examples 1, 2, and Examples 1 - 5 First, the carrier resin (thermoplastic resin (A)) and the processing aid were melt-kneaded at a ratio shown in Table 1 using a twin-screw extruder (TEX25αIII manufactured by Japan Steel Works, Ltd.) 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 the matrix resin (thermoplastic resin (B)) at a ratio such that the concentration of the processing aid in the finally obtained thermoplastic resin composition was constant (2000 ppm), and the processability at that time was evaluated by the following extrusion evaluation. The results are shown in Table 2. 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 in a single-screw extruder (manufactured by HAAKE, Rheomex OS, L / D: 33, screw diameter: 20 mm, die diameter: 2 mm) under the conditions of a cylinder temperature of 170 to 200 °C, a die temperature of 200 °C, and a shear rate of 450 / second, and evaluated by the following items. Before each test run, linear low-density polyethylene containing 15% by mass of silica was charged into the hopper, the screw rotation speed was increased to 150 rpm, and purging was performed for about 15 minutes. Next, the same matrix resin as that used in the test was charged and purged for about 15 minutes, and then the screw rotation speed was returned to 30 rpm and extrusion was performed until the temperature was stabilized. After confirming that the initial pressure had returned, the next experiment was conducted. If the initial pressure did not return, the above purging operation was repeated until the initial pressure returned, and then the next experiment was conducted. (Melt fracture (MF) disappearance time) Using only the matrix resin, extrusion was performed until the pressure was stabilized with melt fracture occurring over the entire surface. Then, the time when the screw became visible thereafter was set to zero, and extrusion was performed for 60 minutes. For examples using a processing aid or masterbatch, these were charged into the hopper at the zero time point. Then, the appearance of the strand at the initial stage of extrusion and the strand at the completion of extrusion was confirmed by visual inspection and palpation. And the time until the MF observed at the initial stage of extrusion disappeared from the zero time point described above was measured. The shorter the time, the better. Those in which the MF did not disappear were denoted as "-".

[0179]

Table 2

Claims

1. A processing aid having a surface free energy of 28.5 mN / m or more and substantially free of fluorine.

2. The processing aid according to Claim 1, having a surface free energy of 29.0 to 55.0 mN / m.

3. The processing aid according to Claim 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) (In formula 1, X is a divalent group which may have a single bond or a functional group, Y and Z are each independently a single bond, -O-, -C(=O)-, -C(=O)O-, -OC(=O)O-, -C(=NR')-, -C(=NR')O-, -OC(=NR')O-, -S-, -S(=O)-, -S(=O)O-, -OS(=O)O-, -S(=O) ２ -, -S(=O) ２ O-, -OS(=O) ２ O-, -P(=O)-, -P(=O)O-, -OP(=O)O-, -P(=O) ２ -, -P(=O) ２ O-, -OP(=O) ２ O-, -NR'-, and -C(OR')R'- (wherein R' is, independently at each occurrence, a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms), and is a group composed of at least one selected from the group consisting of R １ 、R ２ 、R ３ and R ４ are each independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, n and m are each independently an integer of 0 to 10, and at least one of X, Y and Z is -C(=O)-, -C(=O)O-, -OC(=O)O- or -C(OR')R'-. )

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

5. In the formula 1, the processing aid according to Claim 4, wherein X is a divalent group containing at least one selected from the group consisting of -C(=O)-, -CR'R'-, and -C(OR')R'- (wherein R' is independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms in each occurrence).

6. In the formula 1, Y and Z are each independently a single bond, -O-, -C(=O)-, -C(=O)O-, -C(=NR')-, -C(=NR')O-, -S-, -S(=O) ２ -, -S(=O) ２ O-, -NR'-, and -C(OR')R'- (wherein R' is independently, in each occurrence, a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms), and the processing aid according to claim 3, which is a group composed of at least one selected from the group consisting of

7. In the formula 1, the processing aid according to Claim 6, wherein Y and Z are each independently a group composed of at least one selected from the group consisting of a single bond, -O-, -C(=O)-, and -C(=O)O-.

8. The processing aid according to Claim 1 or 2, having a melt flow rate of 0.001 to 100 g / 10 min at 190°C under a load of 2.16 kgf.

9. The processing aid 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.

10. A masterbatch containing the processing aid according to Claim 1 and a thermoplastic resin (A).

11. The masterbatch according to Claim 10, wherein the thermoplastic resin (A) is a polyolefin resin.

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

13. The masterbatch according to Claim 10 or 11, wherein the difference in surface free energy between the processing aid and the thermoplastic resin (A) is 1.5 mN / m or more.

14. The masterbatch according to Claim 10 or 11, wherein the difference in surface free energy between the processing aid and the thermoplastic resin (A) is 4.0 to 45 mN / m.

15. The masterbatch according to claim 10 or 11, wherein the mass ratio of the thermoplastic resin (A) to the processing aid (thermoplastic resin (A): processing aid) is 92:8 to 70:

30.

16. A thermoplastic resin composition comprising the processing aid according to claim 1 or 2 and / or the masterbatch according to claim 10 or 11, and a thermoplastic resin (B).

17. The thermoplastic resin composition according to claim 16, wherein the thermoplastic resin (B) is a polyolefin resin.

18. The thermoplastic resin composition according to claim 16, wherein the thermoplastic resin (B) is a metallocene-catalyzed linear low-density polyethylene.

19. The thermoplastic resin composition according to claim 16, wherein the difference in surface free energy between the processing aid and the thermoplastic resin (B) is 1.5 mN / m or more.

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

21. The thermoplastic resin composition according to claim 16, wherein the content of the processing aid is 0.1 to 1.0% by mass.

22. A molded article using the thermoplastic resin composition according to claim 16.

23. The molded article according to claim 22, which is in a tubular, film or sheet form.

24. A method for producing the processing aid according to claim 1 or 2, comprising a mixing step and an extrusion step.

25. A method for producing the masterbatch according to claim 10 or 11, comprising a mixing step and an extrusion step.

26. A method for producing the thermoplastic resin composition according to claim 16, comprising a mixing step and an extrusion step.

27. A method for producing the molded article according to claim 22, comprising a molding step.

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