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 contains a deterioration preventive agent, and a polyester resin.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 in which 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, Patent Document 1 proposes a method containing ethylene vinyl alcohol, and Patent Document 2 proposes a method containing a surfactant and polyethylene glycol. However, the effect was not sufficient.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0005] An object of the present disclosure is to provide a 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 containing a deterioration inhibitor and a polyester resin.

[0007] The present disclosure (2) is the processing aid described in the present disclosure (1) that substantially does not contain fluorine.

[0008] The present disclosure (3) is the processing aid described in the present disclosure (1) or (2), wherein the deterioration inhibitor contains at least one skeleton selected from the group consisting of a phenol skeleton and a phosphoric acid skeleton.

[0009] The present disclosure (4) is the processing aid according to any one of the present disclosures (1) to (3), wherein the deterioration inhibitor is at least one selected from the group consisting of pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] and tris(2,4-di-tert-butylphenyl) phosphite.

[0010] The present disclosure (5) is the processing aid according to any one of the present disclosures (1) to (4), wherein the melting point of the polyester resin is 190°C or lower.

[0011] The present disclosure (6) is the processing aid according to any one of the present disclosures (1) to (5), wherein the polyester resin is a biodegradable resin.

[0012] The present disclosure (7) is the processing aid according to any one of the present disclosures (1) to (6), wherein the polyester resin is polylactic acid.

[0013] The present disclosure (8) is further the processing aid according to any one of the present disclosures (1) to (7), which contains an ethylene-vinyl alcohol copolymer.

[0014] The present disclosure (9) is a masterbatch containing the processing aid according to any one of the present disclosures (1) to (8) and a thermoplastic resin (A).

[0015] The present disclosure (10) is the masterbatch according to the present disclosure (9), wherein the thermoplastic resin (A) is a polyolefin resin.

[0016] The present disclosure (11) is the masterbatch according to the present disclosure (9) or (10), wherein the thermoplastic resin (A) is at least one selected from the group consisting of metallocene-catalyzed linear low-density polyethylene and Ziegler-Natta-catalyzed linear low-density polyethylene.

[0017] The present disclosure (12) is the masterbatch according to any one of the present disclosures (9) to (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.

[0018] The present disclosure (13) is a thermoplastic resin composition comprising the processing aid according to any one of the present disclosures (1) to (8) and / or the masterbatch according to any one of the present disclosures (9) to (12), and a thermoplastic resin (B).

[0019] The present disclosure (14) is the thermoplastic resin composition according to the present disclosure (13), wherein the thermoplastic resin (B) is a polyolefin resin.

[0020] The present disclosure (15) is the thermoplastic resin composition according to the present disclosure (13) or (14), wherein the thermoplastic resin (B) is metallocene-catalyzed linear low-density polyethylene.

[0021] The present disclosure (16) is the thermoplastic resin composition according to any one of the present disclosures (13) to (15), wherein the content of the processing aid is 0.1 to 1% by mass.

[0022] The present disclosure (17) is a molded article using the thermoplastic resin composition according to any one of the present disclosures (13) to (16).

[0023] The present disclosure (18) is the molded article according to the present disclosure (17), which is in a tubular shape, a film shape, or a sheet shape.

[0024] The present disclosure (19) is the molded article according to the present disclosure (17) or (18), wherein the thickness unevenness calculated by the following formula is 15% or less. Thickness unevenness (%) = (Maximum thickness - Minimum thickness) / Average thickness × 100

[0025] The present disclosure (20) is a method for manufacturing a processing aid described in any one of the present disclosures (1) to (8) including a mixing step and a discharging step.

[0026] The present disclosure (21) is a method for manufacturing a masterbatch described in any one of the present disclosures (9) to (12) including a mixing step and a discharging step.

[0027] The present disclosure (22) is a method for manufacturing a thermoplastic resin composition described in any one of the present disclosures (13) to (16) including a mixing step and a discharging step.

[0028] The present disclosure (23) is a method for manufacturing a molded article described in any one of the present disclosures (17) to (19) including a molding step.

Advantages of the Invention

[0029] According to the present disclosure, the processability of the thermoplastic resin can be improved.

Modes for Carrying Out the Invention

[0030] Hereinafter, the present disclosure will be specifically described.

[0031] <Processing Aid> The thermoplastic resin composition of the present disclosure includes a deterioration inhibitor and a polyester resin.

[0032] According to the processing aid of the present disclosure, good processability can be obtained. In particular, the thickness unevenness of the film during extrusion molding can be improved.

[0033] As the deterioration inhibitor, a compound containing at least one skeleton selected from the group consisting of a phenol skeleton and a phosphoric acid skeleton can be preferably used.

[0034] When the above-mentioned deterioration inhibitor has a phenol skeleton, the number thereof is not particularly limited, but is preferably 1 or more, more preferably 2 or more, still more preferably 3 or more, particularly preferably 4 or more, and is preferably 100 or less, more preferably 10 or less, still more preferably 6 or less.

[0035] Specific examples of the above deterioration inhibitor having a phenol skeleton include compounds having one phenol skeleton (monocyclic phenol compounds) such as 2,6-di-t-butyl-p-cresol, 2,6-di-t-butyl-4-ethylphenol, 2,6-dicyclohexyl-4-methylphenol, 2,6-diisopropyl-4-ethylphenol, 2,6-di-t-amyl-4-methylphenol, 2,6-di-t-octyl-4-n-propylphenol, 2,6-dicyclohexyl-4-n-octylphenol, 2-isopropyl-4-methyl-6-t-butylphenol, 2-t-butyl-4-ethyl-6-t-octylphenol, 2-isobutyl-4-ethyl-6-t-hexylphenol, 2-cyclohexyl-4-n-butyl-6-isopropylphenol, styrenated mixed cresols, DL-α-tocopherol, stearyl β-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 2,6-di-t-butyl-4-(4,6-bis(octylthio)-1,3,5-triazin-2-ylamino)phenol, etc.; compounds having two phenol skeletons (bicyclic phenol compounds) such as 2,2'-methylenebis(4-methyl-6-t-butylphenol), 4,4'-butylidenebis(3-methyl-6-t-butylphenol), 4,4'-thiobis(3-methyl-6-t-butylphenol), 2,2'-thiobis(4-methyl-6-t-butylphenol), 4,4'-methylenebis(2,6-di-t-butylphenol), 2,2'-methylenebis[6-(1-methylcyclohexyl)-p-cresol], 2,2'-ethylidenebis(4,6-di-t-butylphenol), 2,2'-butylidenebis(2-t-butyl-4-methylphenol), 3,6-dioxaoctamethylenebis[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionate], triethylene glycol bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,2'-thiodiethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], etc.Compounds having three phenolic skeletons (tricyclic phenolic compounds) such as 1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane, 1,3,5-tris(2,6-dimethyl-3-hydroxy-4-t-butylbenzyl)isocyanurate, 1,3,5-tris[(3,5-di-t-butyl-4-hydroxyphenyl)propionyloxyethyl]isocyanurate, tris(4-t-butyl-2,6-dimethyl-3-hydroxybenzyl)isocyanurate, 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene; Compounds having four phenolic skeletons (tetracyclic phenolic compounds) such as tetrakis[methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]methane, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], etc. Among them, tetracyclic phenolic compounds are preferred, and tetrakis[methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]methane and pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] are more preferred, and pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] is even more preferred.;

[0036] The phosphate skeleton has a structure in which 1 to 4 O (oxygen atoms) are bonded to 1 P (phosphorus atom). Among them, those in which 3 O (oxygen atoms) are bonded to 1 P (phosphorus atom) are preferred.

[0037] When the above-mentioned deterioration inhibitor has a phosphate skeleton, the number thereof is not particularly limited, but it is preferably 1 or more, more preferably 2 or more, even more preferably 3 or more, and also preferably 100 or less, more preferably 10 or less, even more preferably 6 or less.

[0038] Specific examples of the above-mentioned deterioration inhibitor having a phosphate skeleton include

Chemical formula

[0039] Examples of diphosphorous acid include tetraethyl diphosphite and tetrapropyl diphosphite. Examples of triphosphorous acid include the P,P’-bis(2-hydroxyethyl) ester of triphosphorigenic acid.

[0040] Oligophosphites and polyphosphites (oligomer and polymer phosphites) are described, for example, in International Publication No. 2011 / 102861, International Publication No. 2014 / 20519, International Publication No. 2020 / 123986, etc. Compounds described therein can also be used. Examples include the following compounds.

[0041]

Chemical formula

[0042] In addition, for example, phosphates, diphosphates, metaphosphates, polyphosphates derived from the aforementioned phosphites such as trilauryl phosphate, trisisodecyl phosphate, tridecyl phosphate, trihexadecyl phosphate, trioctadecyl phosphate, tribehenyl phosphate, triarachidyl phosphate, triceryl phosphate, trioleyl phosphate, and the following structures and salts derived therefrom, and at least two phosphates selected from the group consisting of monoalkyl phosphates, dialkyl phosphates, and trialkyl phosphates are also included.

[0043]

Chemical formula

[0044] In the case of the aforementioned phosphates, diphosphates, metaphosphates, and polyphosphates which are derivatives of the aforementioned phosphites, the phosphorus atom exists at an oxidation number of +V rather than +III as in the case of phosphites.

[0045] As the above-mentioned deterioration inhibitor having a phosphate backbone, phosphite is preferable. Examples of phosphites include the following compounds.

[0046]

Chemical formula

[0047]

Chemical formula

[0048]

Chemical formula

[0049] In addition, a particularly preferred phosphite is tris(2,4-di-tert-butylphenyl) phosphite.

[0050] Specific examples of the above-mentioned deterioration inhibitor having a phenol skeleton and a phosphoric acid skeleton include phosphorus-containing phenol compounds such as calcium bis(3,5-di-t-butyl-4-hydroxybenzylphosphonate) and nickel bis(3,5-di-t-butyl-4-hydroxybenzylphosphonate).

[0051] The above-mentioned deterioration inhibitor may have only either a phenol skeleton or a phosphoric acid skeleton, or may have both a phenol skeleton and a phosphoric acid skeleton, but those having only either a phenol skeleton or a phosphoric acid skeleton are preferred.

[0052] It is preferable to use in combination the above-mentioned deterioration inhibitor with a compound having only a phenol skeleton (phenolic deterioration inhibitor) and a compound having only a phosphoric acid skeleton (phosphoric acid-based deterioration inhibitor). Thereby, the pressure stability during extrusion becomes good.

[0053] When using in combination a phenolic deterioration inhibitor and a phosphoric acid-based deterioration inhibitor as the above-mentioned deterioration inhibitor, the mass ratio thereof (phenolic deterioration inhibitor: phosphoric acid-based deterioration inhibitor) is preferably 20:80 to 80:20. The above mass ratio is more preferably 30:70 to 70:30, still more preferably 40:60 to 60:40, and particularly preferably 50:50.

[0054] In the processing aid of the present disclosure, the content of the above-mentioned deterioration inhibitor is preferably 10% by mass or more, more preferably 20% by mass or more, still more preferably 30% by mass or more, and preferably 80% by mass or less, more preferably 70% by mass or less, still more preferably 60% by mass or less.

[0055] Examples of the polyester resin include biodegradable resins such as polylactic acid (PLA), polybutylene succinate (PBS), polybutylene succinate adipate (PBSA), polyhydroxybutyrate, polycaprolactone, polybutylene succinate / adipate, polyethylene succinate, poly(lactic acid), polyglycolic acid, polydioxanone, and poly(2-oxetanone); and aromatic aliphatic polyesters such as polybutylene succinate / terephthalate, polybutylene adipate / terephthalate (PBAT), and polytetramethylene adipate / terephthalate. These may be used alone or in combination of two or more. From the viewpoint of more favorable improvement effect on processability, biodegradable aliphatic polyesters are preferred, at least one selected from the group consisting of PLA, PBS, and PBSA is more preferred, at least one selected from the group consisting of PLA and PBS is still more preferred, and PLA is even more preferred. In addition, as the polyester resin, the above biodegradable resin can be preferably used.

[0056] The melting point of the above polyester resin 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, and still more preferably 180°C or lower. Within the above range, the improvement effect on processability is more favorable. 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.

[0057] The melt flow rate (MFR) of the above polyester resin is preferably 0.001 g / 10 min or more, more preferably 0.01 g / 10 min or more, still more preferably 0.05 g / 10 min or more, even more preferably 0.1 g / 10 min or more, particularly preferably 0.5 g / 10 min or more. Also, it is preferably 500 g / 10 min or less, more preferably 300 g / 10 min or less, still more preferably 150 g / 10 min or less, even more preferably 40 g / 10 min or less, even more preferably 20 g / 10 min or less, particularly preferably 10 g / 10 min or less. If it is within the above range, the effect of improving processability will be 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.

[0058] From the viewpoint of improving processability, the weight average molecular weight of the above polyester resin is preferably 80,000 or more, more preferably 100,000 or more. From the same viewpoint, it is preferably 400,000 or less, more preferably 350,000 or less. The weight average molecular weight of the above resin (A) can be determined by using gel permeation chromatography (GPC), with chloroform as the solvent, a high-temperature SEC column (GMHHR-H series) manufactured by Tosoh Corporation for the column, a flow rate of 1.0 mL / min, a column temperature of 40 °C, a differential refractive index detector (RI) for the detector, and polystyrene having a known molecular weight as a reference for conversion.

[0059] In the processing aid of the present disclosure, the content of the above polyester resin is preferably 20% by mass or more, more preferably 30% by mass or more, still more preferably 40% by mass or more. Also, it is preferably 90% by mass or less, more preferably 80% by mass or less, still more preferably 70% by mass or less.

[0060] In the processing aid of the present disclosure, the total content of the above antioxidant and the above polyester resin is preferably 60% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more. The upper limit is not particularly limited and may be 100% by mass, but it is preferably 99% by mass or less, more preferably 98% by mass or less.

[0061] The processing aid of the present disclosure preferably contains an ethylene-vinyl alcohol copolymer (EVOH) together with the above-mentioned deterioration inhibitor and the above-mentioned polyester resin. Thereby, better processability can be obtained.

[0062] The ethylene content of the above-mentioned ethylene-vinyl alcohol copolymer is preferably 10 mol% or more, more preferably 20 mol% or more, still more preferably 30 mol% or more, and preferably 60 mol% or less, more preferably 50 mol% or less, still more preferably 40 mol% or less. Within the above range, the effect of improving processability becomes better. In this specification, the ethylene content is determined by nuclear magnetic resonance (NMR) method.

[0063] The above-mentioned ethylene-vinyl alcohol copolymer is preferably obtained by saponifying an ethylene-vinyl ester copolymer, and among them, one obtained by saponifying an ethylene-vinyl acetate copolymer is particularly preferable.

[0064] The saponification degree of the above-mentioned ethylene-vinyl alcohol copolymer is preferably 80 to 100 mol%.

[0065] When copolymerizing ethylene and vinyl acetate, other vinyl fatty acid esters (such as vinyl propionate and vinyl pivalate) can also be used in combination. Further, the ethylene-vinyl alcohol copolymer can 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.

[0066] When copolymerizing ethylene and vinyl acetate, monomers other than the above-mentioned vinyl fatty acid esters and vinyl silane compounds can also be present in a small amount, such as α-olefins like propylene, isobutylene, α-octene, α-dodecene, etc.; unsaturated acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid or their anhydrides, salts, or mono- or dialkyl esters, etc.; nitriles such as acrylonitrile, methacrylonitrile, etc.; amides such as acrylamide, methacrylamide, etc.; olefin sulfonic acids such as ethylene sulfonic acid, allyl sulfonic acid, methallyl sulfonic acid or their salts; alkyl vinyl ethers, vinyl ketones, N-vinyl pyrrolidone, vinyl chloride, vinylidene chloride, etc.

[0067] In the processing aid of the present disclosure, the content of the above ethylene-vinyl alcohol copolymer is preferably 3% by mass or more, more preferably 5% by mass or more, still more preferably 6% by mass or more, and preferably 90% by mass or less, more preferably 70% by mass or less, still more preferably 50% by mass or less.

[0068] The mass ratio of the above polyester resin to the above ethylene-vinyl alcohol copolymer (polyester resin: ethylene-vinyl alcohol copolymer) is preferably 99:3 to 10:90. The above mass ratio is more preferably 95:5 to 70:30, still more preferably 92:8 to 50:50, and particularly preferably 90:10 to 75:25.

[0069] In the processing aid of the present disclosure, the total content of the above antioxidant, the above polyester resin and the above ethylene-vinyl alcohol copolymer is preferably 80% by mass or more, more preferably 90% by mass or more, and particularly preferably 100% by mass.

[0070] The processing aid of the present disclosure may contain other components in addition to the above-mentioned deterioration inhibitor, the above-mentioned polyester resin, and the above-mentioned ethylene-vinyl alcohol copolymer. Examples of the other components include a polyol having a melting point of 80°C or lower, and at least one synergist selected from the group consisting of polycaprolactone, silicone, and polyamide-polyether block copolymer.

[0071] The melting point of the above polyol may be 80°C or lower, preferably 75°C or lower, more preferably 70°C or lower, still more preferably 68°C or lower, and preferably 10°C or higher, more preferably 20°C or higher, still more preferably 25°C or higher. Within the above range, the effect of improving processability is better.

[0072] The above polyol can be represented, for example, by A[(OR 11 ) x OR 12 y , where A is usually an alkylene having one or more ether bonds, y is 2 or 3, and (OR 11 ) x is a poly(oxyalkylene) chain having a plurality (x) of oxyalkylene groups OR 11 , R 11 are each independently C2-C5 alkylene, and in some embodiments, C2-C3 alkylene, and R 12 is hydrogen, alkyl, aryl, arylalkenyl, alkylarylenyl, -C(O)-alkyl, -C(O)-aryl, -C(O)-arylalkenyl or -C(O)-alkylarylenyl, and -C(O)- is bonded to the O of OR 12 . x is from 10 to 230,000.

[0073] The above polyol can be a homopolymer of poly(oxypropylene) in which R 11 is -CH2CH2-, or a homopolymer of poly(oxyethylene) in which R 11 is -C3H6-, etc.

[0074] ​ The above polyol may have a chain composed of randomly distributed oxyalkylene groups (for example, -OC2H4- and -OC3H6- units which are copolymers), or an alternating block composed of repeating oxyalkylene groups (for example, (-OC2H4-) a1 block and (-OC3H6-) b1 block), and a1 + b1 is a number from 10 to 230,000).

[0075] 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.

[0076] The above polyol is a polyester prepared from a dicarboxylic acid and a poly(oxyalkylene) polymer represented by A[(OR 11 ) x2 OR 12 y2 , where A, R 11 and x2 are as defined above, and R 12 is hydrogen and y2 is 2.

[0077] The above polyol may be used alone or in combination of two or more. From the viewpoint of excellent improvement effect on processability, polyethylene glycol and polyethylene oxide are preferred, and polyethylene glycol is particularly preferred.

[0078] ​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.

[0079] 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 c 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

[0080] The above polycaprolactone may be a homopolymer of ε-caprolactone or a modified polycaprolactone. Examples of the above modified polycaprolactone include those modified by coexisting with 1,4-butanediol or the like during the ring-opening polymerization of ε-caprolactone, and those modified with an ether or ester group or the like at the terminal of the polymer.

[0081] The weight average molecular weight (Mw) of the above polycaprolactone is preferably 2,000 or more, more preferably 10,000 or more, still more preferably 25,000 or more, and is preferably 100,000 or less, more preferably 95,000 or less, still more preferably 90,000 or less. Within the above range, the effect of improving processability is better. In this specification, the weight average molecular weight is measured by polystyrene conversion using gel permeation chromatography (GPC) method.

[0082] The melting point of the above polycaprolactone is preferably 80°C or less, more preferably 75°C or less, still more preferably 70°C or less, even more preferably 68°C or less, and is preferably 10°C or more, more preferably 20°C or more, still more preferably 45°C or more. Within the above range, the effect of improving processability is better.

[0083] In principle, the above silicone can 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.

[0084] Silicone can be a substituted or unsubstituted linear oligo- or polydiorganosiloxane, a branched silicone polymer, a silicone resin or a cross-linked silicone polymer. Naturally, mixtures consisting of various silicone polymers can also be used. As already mentioned, silicone-containing copolymers, for example 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 which can also contain non-silicone components, such as fillers like particulate silicic acid, chalk, talc and sheet silicates, is particularly preferred.

[0085] 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.

[0086] 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, especially methyl residues, are preferred.

[0087] R 13 Examples of the residue R also include unsaturated C1 to C18 hydrocarbon residues such as alkenyl residues such as vinyl residues, 2-propen-2-yl residues, allyl residues, 3-buten-1-yl residues, 5-hexen-1-yl residues, 10-undecen-1-yl residues, and cycloalkenyl residues (2-cyclohexenyl residues, 3-cyclohexenyl residues, cyclopentadienyl residues, 2-(cyclohexa-3-en-1-yl)ethyl residues); aryl residues such as phenyl residues, biphenylyl residues and naphthyl residues; alkaryl residues such as o-, m- and p-tolyl residues and phenethyl residues (2-phenylethyl residues, 1-phenylethyl residues) and aralkyl residues such as benzyl residues. Preferred unsaturated C1 to C18 hydrocarbon residues R 13 are vinyl residues and phenyl residues.

[0088] Residue R 13 Examples of the substituted hydrocarbon residue as the 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.

[0089] Residue R 13 is preferably bonded to the silicone polymer represented by formula A via an Si-C bond, but can also be bonded to the silicone polymer via an oxygen atom -O-.

[0090] 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.

[0091] 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.

[0092] Preferably, c2 + d2 means < 0.1×(a2 + b2 + c2 + d2), particularly c2 + d2 < 0.05×(a2 + b2 + c2 + d2).

[0093] Preferably, all residues R 13 at least 50%, more preferably at least 70%, particularly preferably at least 80% thereof mean methyl residues.

[0094] 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.

[0095] 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, pp. 7-19) may be used.

[0096] 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.

[0097] Typical UHMW polysiloxanes preferably have a dynamic viscosity between 10 kPa·s and 50 kPa·s, preferably between 15 kPa·s and 30 kPa·s, measured with an air-suspended rotational rheometer in accordance with DIN EN ISO 3219:1994 and DIN 53019, where a plate-plate system (diameter 25 mm) with a measuring gap of 0.5 mm is used. The measurement temperature is 25.00 °C + / - 0.1 °C. The shear rate gradient is 0.1 sec -1 -1. The viscosity description represents the arithmetic mean value of three individually performed measurements.

[0098] 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.

[0099] The above-mentioned UHMW polysiloxane includes commercially available UHMW polysiloxanes such as MULTIBASE (registered trademark) MB50-001 and MULTIBASE (registered trademark) MB50-002 manufactured by Dupont, GENIOPLAST (registered trademark) PELLET S, GENIOPLAST (registered trademark) PELLET P PlUS, GENIOPLAST (registered trademark) PE50S08, GENIOPLAST (registered trademark) PP50S12, and mixtures thereof. MB50-002 and GENIOPLAST (registered trademark) PELLET S are preferred.

[0100] Silicone polymers are commercially available in the form of pellets / granules or masterbatches, and can be used immediately, for example, they can be mixed with thermoplastic plastic granules before these further processes.

[0101] The above-mentioned polyamide-polyether block copolymer is a copolymer having a polyamide block and a polyether block in the polymer backbone. In the present disclosure, such a block copolymer having a polyamide block and a polyether block can also be referred to as a "polyamide / polyether block copolymer". Also, it can be abbreviated as "PEBA copolymer" or "PEBA". In some embodiments of the present disclosure, the PEBA copolymer can be represented by the following general formula.

Chemical formula

[0102] Here, PA is a polyamide block, PE is a polyether block, p represents the length of the PEBA copolymer, and represents the total number of polyamide and polyether blocks. In some embodiments of the present disclosure, the PEBA copolymer can be represented by the following general formula.

Chemical formula

[0103] Here, EG is a first unspecified end group, B is an unspecified crosslinking group, and EG * is a second unspecified end group, and EG, B, and EG * are determined by the synthesis method used to produce the PEBA copolymer. Here, n2 represents the length of the polyamide block, x3 represents the length of the amide component within the polyamide block, m1 represents the length of the poly(ether) block, y3 represents the length of the ether component within the poly(ether) block, p represents the length of the PEBA copolymer, and represents the total number of polyamide and polyether blocks. In some embodiments of the present disclosure, the PEBA copolymer can be represented by the following general formula.

Chemical formula

[0104] Here, n2 represents the length of the polyamide block, x3 represents the length of the amide component within the polyamide block, m1 represents the length of the poly(ether) block, y3 represents the length of the ether component within the poly(ether) block, p represents the length of the PEBA copolymer, and represents the total number of polyamide and polyether blocks.

[0105] 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).

[0106] 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.

[0107] In an embodiment, the number average molecular weight Mn of the polyamide block in the PEBA copolymer is from about 100 to about 15,000 g / mol, or from about 300 to about 15,000 g / mol, or from about 600 to about 10,000 g / mol, or from about 600 to about 5,000 g / mol. The number average molecular weight Mn of the polyether block in the PEBA copolymer is from about 100 to about 15,000 g / mol, from about 100 to about 10,000 g / mol, from about 100 to about 6,000 g / mol, from about 100 to about 3,000 g / mol, from about 200 to about 6,000 g / mol, from about 200 to about 3,000 g / mol, from about 250 to about 2,000 g / mol, from about 750 to about 3,500 g / mol, or from about 1,000 to about 3,000 g / mol.

[0108] The number average molecular weight Mn of the PEBA copolymer is from 10,000 to 500,000 g / mol, including sub-ranges within this range and any numbers within this range. For example, in embodiments 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, 10,000 to 250,000 g / mol, or from 15,000 to 300,000 g / mol, or from 20,000 to 300,000 g / mol, or from 15,000 to 200,000 g / mol, or from 20,000 to 200,000 g / mol, or from 30,000 to 250,000 g / mol, or from about 25,000 to about 75,000 g / mol, or from about 50,000 to about 75,000 g / mol, or from about 100,000 to about 150,000 g / mol. The number average molecular weight Mn of the PEBA copolymer is at least 10,000 g / mol, at least 20,000 g / mol, at least 25,000 g / mol, more than 25,000 g / mol, at least 30,000 g / mol, more than 30,000 g / mol, at least 35,000 g / mol, more than 35,000 g / mol, at least 50,000 g / mol, or more than 50,000 g / mol.

[0109] In an embodiment, the weight average molecular weight Mw of the PEBA copolymer is from 25,000 to 500,000 g / mol, including sub - ranges within this range and any number within this range. For example, in embodiments of the present disclosure, the weight average molecular weight Mw of the PEBA copolymer is from about 100,000 to about 250,000 g / mol, or from about 100,000 to about 150,000 g / mol, or from about 125,000 to about 150,000 g / mol. The polyamide and polyether blocks within the above - mentioned PEBA copolymer can be randomly distributed.

[0110] The above - mentioned 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 - mentioned 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.

[0111] By reacting the above - mentioned 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 in 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 in 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).

[0112] 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.

[0113] The above-mentioned PEBA copolymer comprises i) a polyamide block selected from polyamide-12 (PA-12), polyamide-11 (PA-11), polyamide-6 (PA-6), or a mixture thereof, and ii) a polyether block which is polyethylene glycol (PEG). In one embodiment of the present disclosure, the PEBA copolymer comprises i) a polyamide block which is polyamide-12 (PA-12), and ii) a polyether block which is polyethylene glycol (PEG).

[0114] The above-mentioned PEBA copolymer contains 10 to 20 polyamide blocks and 10 to 20 polyether blocks.

[0115] The above-mentioned PEBA copolymer contains only one type of polyamide block and one type of polyether block.

[0116] The above-mentioned PEBA copolymer comprises i) a polyamide block which is polyamide-12 (PA-12), and ii) a polyether block which is polyethylene glycol (PEG), wherein the polyamide-12 block accounts for about 30% to 70% by mass of the copolymer, and the polyethylene glycol block accounts for about 70% to 30% by mass of the copolymer.

[0117] The above-mentioned PEBA copolymer comprises i) a polyamide block which is polyamide-12 (PA-12), and ii) a polyether block which is polyethylene glycol (PEG), wherein the polyamide-12 block accounts for about 40% to 60% by mass of the copolymer, and the polyethylene glycol block accounts for about 60% to 40% by mass of the copolymer.

[0118] The above-mentioned PEBA copolymer comprises i) a polyamide block which is polyamide-12 (PA-12) and ii) a polyether block which is polyethylene glycol (PEG), wherein the polyamide-12 block represents about 45% by mass of the copolymer, and the polyethylene glycol block represents about 55% by mass of the copolymer.

[0119] The above-mentioned PEBA copolymer contains i) 10 to 20 polyamide blocks which are polyamide-12 (PA-12), and ii) 10 to 20 polyether blocks which are polyethylene glycol (PEG).

[0120] The above-mentioned PEBA copolymer contains i) a polyamide block which is polyamide-12 (PA-12), and ii) a polyether block which is polyethylene glycol (PEG), and has a number-average molecular weight Mn of about 25,000 to about 75,000 g / mol.

[0121] The above-mentioned PEBA copolymer contains i) a polyamide block which is polyamide-12 (PA-12), and ii) a polyether block which is polyethylene glycol (PEG), and 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 which is polyamide-12 (PA-12) and ii) a polyether block which is polyethylene glycol (PEG), and has a number-average molecular weight Mn of about 66,100 g / mol.

[0122] The above-mentioned PEBA copolymer contains i) a polyamide block which is polyamide-12 (PA-12), and ii) a polyether block which is polyethylene glycol (PEG), and has a weight-average molecular weight Mw of about 100,000 to about 150,000 g / mol.

[0123] The above-mentioned PEBA copolymer contains i) a polyamide block which is polyamide-12 (PA-12), and ii) a polyether block which is polyethylene glycol (PEG), and has a weight-average molecular weight Mw of about 125,000 to about 150,000 g / mol.

[0124] The above-mentioned PEBA copolymer contains i) a polyamide block which is polyamide-12 (PA-12) and ii) a polyether block which is polyethylene glycol (PEG), and has a weight-average molecular weight Mw of about 134,000 g / mol.

[0125] In one embodiment of the present disclosure, the PEBA copolymer comprises i) a polyamide block that is polyamide-6 (PA-6), and ii) a polyether block that is polyethylene glycol (PEG). The PEBA copolymer comprises i) a polyamide block that is polyamide-6 (PA-6) and ii) a polyether block that is polyethylene glycol (PEG), wherein the polyamide-6 block represents 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.

[0126] The PEBA copolymer comprises i) a polyamide block that is polyamide-6 (PA-6) and ii) a polyether block that is polyethylene glycol (PEG), wherein the polyamide-6 block represents 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.

[0127] The PEBA copolymer comprises 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).

[0128] The PEBA copolymer comprises i) a polyamide block that is polyamide-11 (PA-11), and ii) a polyether block that is polyethylene glycol (PEG). In one embodiment of the present disclosure, the PEBA copolymer comprises i) a polyamide block that is polyamide-12 (PA-12), and ii) a polyether block that is polytetrahydrofuran (PTHF).

[0129] The above-mentioned PEBA copolymer contains i) a polyamide block which is polyamide-12 (PA-12), and ii) a polyether block which is polytetrahydrofuran (PTHF), where the polyamide-12 block represents from about 75% to 10% by mass of the copolymer, and the polytetrahydrofuran block represents from about 25% to 90% by mass of the copolymer.

[0130] The above-mentioned PEBA copolymer contains i) a polyamide block which is polyamide-12 (PA-12), and ii) a polyether block which is polytetrahydrofuran (PTHF), where the polyamide-12 block represents from about 80% to 60% by mass of the copolymer, and the polytetrahydrofuran block represents from about 20% to 40% by weight of the copolymer.

[0131] The above-mentioned PEBA copolymer contains i) a polyamide block which is polyamide-12 (PA-12), and ii) a polyether block which is polytetrahydrofuran (PTHF), where the polyamide-12 block represents from about 40% to 60% by mass of the copolymer, and the polytetrahydrofuran block represents from about 60% to 40% by mass of the copolymer.

[0132] The above-mentioned PEBA copolymer contains i) a polyamide block which is polyamide-12 (PA-12), and ii) a polyether block which is polytetrahydrofuran (PTHF), where the polyamide-12 block represents from about 30% to 10% by mass of the copolymer, and the polytetrahydrofuran block represents from about 70% to 90% by mass of the copolymer. The above-mentioned PEBA copolymer contains i) 10 to 20 polyamide blocks which are polyamide-12 (PA-12), and ii) 10 to 20 polyether blocks which are polytetrahydrofuran (PTHF).

[0133] The above-mentioned PEBA copolymer includes i) a polyamide block which is polyamide-12 (PA-12) and ii) a polyether block which is polytetrahydrofuran (PTHF), and has a number-average molecular weight Mn of about 25,000 to about 75,000 g / mol. The above-mentioned PEBA copolymer includes i) a polyamide block which is polyamide-12 (PA-12) and ii) a polyether block which is polytetrahydrofuran (PTHF), and has a number-average molecular weight Mn of about 40,000 to about 60,000 g / mol. In an embodiment of the present disclosure, the PEBA copolymer includes i) a polyamide block which is polyamide-12 (PA-12) and ii) a polyether block which is polytetrahydrofuran (PTHF), and has a number-average molecular weight Mn of about 50,000 g / mol.

[0134] The above-mentioned PEBA copolymer includes i) a polyamide block which is polyamide-6 (PA-6), and ii) a polyether block which is polytetrahydrofuran (PTHF). The above-mentioned PEBA copolymer includes i) a polyamide block which is polyamide-11 (PA-11), and ii) a polyether block which is polytetrahydrofuran (PTHF). The above-mentioned PEBA copolymer is a commercially available elastomer and is sold under the trade name PEBAX®.

[0135] 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 (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 trade names VESTAMID® or VESTAMID E.

[0136] 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.

[0137] 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.

[0138] 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 ones; nucleating agents such as metal salts and acetals of sorbitol, and anti-blocking agents can also be used.

[0139] The processing aids of the present disclosure preferably contain substantially no fluorine. "Containing substantially no fluorine" means that the fluorine content in the above-mentioned processing aids is 10 ppm or less (preferably 1 ppm or less, more preferably 0.1 ppm or less). It is particularly preferred that the processing aids of the present disclosure do not contain fluorine (the fluorine content is 0% by mass).

[0140] 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.

[0141] 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 find the average, and adopt the average value. Water content (% by 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

[0142] 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. Alternatively, after preparing the heat processing aid with ordinary materials and conditions, the water may be removed by heat treatment or the like.

[0143] The processing aid of the present disclosure may be obtained, for example, by performing a mixing step of charging the above surfactant (A) and the above resin (B) 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.

[0144] 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. However, from the viewpoint of the effect of improving processability, kneading is preferred, and melt kneading is more preferred. In addition, when performing melt kneading, each component may be melted in the mixing step, or may be melted before the mixing step.

[0145] In the above manufacturing method, after the discharging step, a forming step of forming the discharged material with a molding machine or the like may be performed. The method of the above-mentioned molding process is not particularly limited, and examples thereof include extrusion molding, injection molding, blow molding, etc. Among them, in order to effectively exhibit the above-mentioned moldability, extrusion molding is preferable.

[0146] For the above-mentioned extrusion molding, an extruder is used. Examples of the above-mentioned extruder include a single-screw extruder, a twin-screw extruder, a tandem extruder, etc. The above-mentioned extruder usually 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.

[0147] The various conditions related to the above-mentioned 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.

[0148] The processing aid of the present disclosure is particularly useful as a processing aid for thermoplastic resins (especially polyolefin resins).

[0149] <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, or may be added in the state of a masterbatch.

[0150] As the above-mentioned thermoplastic resin (A), for example, 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. may be mentioned. 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.

[0151] Among the polyolefin polymers, for example, homopolymers (for example, homopolymers of C2 to C10 α-olefins, preferably C2 to C6 α-olefins) may be mentioned. Specific examples of homopolymers include homopolyethylene and polypropylene (hPP). For example, taking homopolyethylene as an example, such a polymer can be produced, for example, by free radical polymerization in a high-pressure process, and is typically a highly branched ethylene homopolymer, often known as LDPE (low-density polyethylene), with a density less than 0.945 g / cm 3 and often less than 0.935 g / cm 3 and, for example, 0.900, 0.905, or 0.910 g / cm 3 to 0.920, 0.925, 0.927, 0.930, 0.935, or 0.945 g / cm 3 within the range. Unless otherwise specified in this specification, all polymer density values are determined in accordance with ASTM D1505. The sample is molded under ASTM D4703-10a, Procedure C, and left standing for 40 hours under ASTM D618-08 (23 ± 2°C and relative humidity 50 ± 10%) before testing.

[0152] In another example, ethylene monomers can be polymerized using known gas, slurry, and / or solution phase polymerization, such as catalysts like chromium-based catalysts, or single-site catalysts like Ziegler-Natta and / or metallocene catalysts, all of which are well-known in the polymerization art and will not be discussed further herein. When a more highly linear ethylene homopolymer is produced (e.g., using gas phase or slurry phase polymerization with any of the above catalysts), it is called HDPE (high density polyethylene) and typically has a density in the range of 0.945 to 0.970 g / cm 3 as, 0.945 g / cm 3 or higher.

[0153] Further examples of polymers include copolymers of two or more C2-C40 α-olefins, such as C2-C20 α-olefins, such as ethylene-α-olefin copolymers, or propylene-α-olefin copolymers (e.g., propylene-ethylene copolymers or propylene-ethylene-diene terpolymers (sometimes known as EPDM or PEDM)). Specific examples contemplated herein include copolymers of ethylene and one or more C3-C20 α-olefin comonomers (1-butene, 1-hexene, 1-octene, or mixtures of two or more thereof being preferred in various embodiments), such as one or more C3-C20 α-olefin comonomers. Ethylene copolymers (e.g., copolymers of ethylene and one or more C3-C20 α-olefins) can contain at least 90, 94, 95, or 96 wt% (e.g., in the range 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%), 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 above low values to any of the above high values. For example, the ethylene copolymer can contain 94 or 95 wt% to 97 or 98 wt% of ethylene-derived units, based on the total amount of ethylene-derived units and comonomer-derived units. The balance of the copolymer (based on ethylene-derived units and comonomer-derived units) consists of comonomer-derived units. For example, comonomer units (e.g., units derived from C2-C20 α-olefins such as units derived from butene, hexene, and / or octene) can be present in the ethylene copolymer in an amount from a low value of 2, 2.5, 3, 3.5, 4, 4.5, 5, or 6 wt% to a high value of 3, 4, 5, 6, 7, 8, 9, 10, 15, or 20 wt%, the range being from the above low value to the above intended high value (provided the high value is greater than the low value).

[0154] 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 as needed. Examples of suitable comonomers include linear C3-C20 α-olefins (such as butene, hexene, octene, etc. as already described), 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.

[0155] In certain embodiments, the polymer can comprise 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 are polymerized in the presence of one or more single-site catalysts, such as one or more Ziegler-Natta catalysts, one or more metallocene catalysts, and combinations thereof. Such LLDPE has a density of 0.900, 0.905, 0.907, 0.910 g / cm 3from a low concentration of 0.920, 0.925, 0.930, 0.935, 0.940, or 0.945 g / cm 3 can have a density within the range of high concentration. LLDPE can be distinguished from the above-mentioned LDPE in several respects, many of which are well-known in the art, including (even if there is little) the degree of branching in the produced polymer. 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).

[0156] Also, in some embodiments, the density of the polymer is in the range of 0.905 to 0.945 g / cm 3 For example, from any of the low values of 0.905, 0.907, 0.908, 0.910, 0.911, 0.912, 0.913, 0.914, or 0.915 g / cm 3 to any of the high values of 0.916, 0.917, 0.918, 0.919, 0.920, 0.924, 0.926, 0.930, 0.935, 0.940, or 0.945 g / cm 3 within the range, and the range is from the above-mentioned low value to the high value 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 .

[0157] Furthermore, the rheological properties of the polymer can affect the processing aid composition for molding the molded article. Generally, the PPA composition is preferably used in a polymer having a melt index (MI or I2, measured at 190°C and a load of 2.16 kg according to ASTM D1238) 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 and a load of 21.6 kg) to the melt index, or HLMI / MI) can generally have an MIR in the range of 10, 12, or 15 to 19, 20, 21, 22, 25, 27, 30, 35, 40, 45, 50, 60, 65, 70, 75, 80, 85, 90, 95, or 100 in the polymers of some embodiments. Optionally, the MI in such polymers can be less than 1.5 g / 10 min, such as less than 1.0 g / 10 min (e.g., from 0.1, 0.2, or 0.5 g / 10 min to 1.0; or any of 1.1, 1.2, 1.3, 1.4, or less than 1.5 g / 10 min).

[0158] 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.

[0159] 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) with a melting point range indicated.

[0160] In the masterbatch of the present disclosure, the mass ratio of the thermoplastic resin (A) to the processing aid (thermoplastic resin (A): processing aid) is preferably from 99:1 to 1:99. The mass ratio is more preferably from 97:3 to 50:50, still more preferably from 95:5 to 60:40, and particularly preferably from 92:8 to 70:30.

[0161] In the masterbatch of the present 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, still more preferably 95% by mass or more, and particularly preferably 100% by mass.

[0162] The melt flow rate (MFR) of the masterbatch of the present disclosure is preferably 0.1 g / 10 min or more, more preferably 0.5 g / 10 min or more, still more preferably 1 g / 10 min or more, even more preferably 1.5 g / 10 min or more, and preferably 100 g / 10 min or less, more preferably 50 g / 10 min or less, still more preferably 30 g / 10 min or less, even more preferably 20 g / 10 min or less, and particularly preferably 10 g / 10 min or less. Within the above range, the effect of improving processability is better.

[0163] The masterbatch of the present disclosure may contain components other than the thermoplastic resin (A) and the processing aid. Examples of the components other than the thermoplastic resin (A) and the processing aid include, 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 a mineral and a flake; a lubricant such as silicone oil and molybdenum disulfide; a pigment such as titanium dioxide and a valve handle; a conductive agent such as carbon black; an impact resistance improver such as rubber; an antioxidant such as a hindered phenol type and a phosphorus type; a nucleating agent such as a metal salt and an acetal of sorbitol, and an anti-blocking agent can be used.

[0164] The masterbatch of the present disclosure may be obtained, for example, by previously preparing the processing aid of the present disclosure, charging it into a mixer or the like together with the above-mentioned thermoplastic resin (A), and performing a mixing step of mixing, and a discharging step of discharging the mixture from the mixer or the like. It may also be obtained by charging the above-mentioned thermoplastic resin (A), the above-mentioned anti-degradant, and the above-mentioned polyester resin 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-mentioned masterbatch including a mixing step and a discharging step.

[0165] In the method for producing the masterbatch 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.

[0166] 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.

[0167] The masterbatch of the present disclosure is particularly useful as a masterbatch for improving the processability of thermoplastic resins (especially polyolefin resins).

[0168] <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, the thickness unevenness during extrusion molding can be improved.

[0169] 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.

[0170] 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, but from the viewpoint of obtaining better processability, it is preferable to contain the masterbatch of the present disclosure.

[0171] When the thermoplastic resin composition of the present disclosure contains the masterbatch of the present disclosure, the above thermoplastic resin (A) and the above thermoplastic resin (B) may be of the same type or different types.

[0172] In the thermoplastic resin composition of the present disclosure, the content of the above 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, particularly preferably 0.1% by mass or more, and is preferably 5% by mass or less, more preferably 3% by mass or less, still more preferably 2% by mass or less, particularly preferably 1% by mass or less.

[0173] The thermoplastic resin composition of the present disclosure may contain components other than the above processing aid, the above masterbatch, and the above thermoplastic resin (B). Examples of components other than the above processing aid, the above masterbatch, and the above thermoplastic resin (B) include, for example, anti-blocking 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 stems; conductive agents such as carbon black; impact resistance improvers such as rubber; antioxidants such as hindered phenol-based and phosphorus-based ones; nucleating agents such as metal salts and acetals of sorbitol; and anti-blocking agents can be used.

[0174] The thermoplastic resin composition of the present disclosure may be obtained, for example, by performing a mixing step of previously preparing the masterbatch of the present disclosure, charging it into a mixer or the like together with the above thermoplastic resin (B), and mixing, and a discharging step of discharging the mixture from the mixer or the like, or by performing a mixing step of charging the above thermoplastic resin (B), the above deterioration inhibitor, and the above polyester resin, and, if necessary, the above thermoplastic resin (A) into a mixer or the like and 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 the mixing step and the discharging step.

[0175] 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.

[0176] 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.

[0177] <Molded article> The molded article of the present disclosure uses the thermoplastic resin composition of the present disclosure, and for example, it may be obtained 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 a molded article in a tube shape, film shape, or sheet shape, but is also applicable to molded articles of other shapes.

[0178] The above molding step is the same as that described in the method for producing the processing aid of the present disclosure.

[0179] In the above molding step, the molding temperature (extrusion temperature) during molding is generally performed at a temperature equal to or higher than the melting point of the above thermoplastic resin (B) and lower than the decomposition temperature of the above deterioration inhibitor and lower than the decomposition temperature of the above polyester resin. In terms of the point where the effect of the above processing aid is significantly exerted, it is preferably in the range of 160°C or higher and 270°C or lower. In the case of extrusion molding, the above molding temperature may be referred to as the extrusion temperature.

[0180] The molded article of the present disclosure preferably has a thickness unevenness calculated by the following formula of 15% or less, more preferably 14% or less, particularly preferably 11% or less, and most preferably 8% or less. The lower limit is not particularly limited and may be 0%. Thickness unevenness (%) = (maximum thickness - minimum thickness) / average thickness × 100 Note that the maximum thickness, minimum thickness, and average thickness in the formula are those measured by the method of the examples.

[0181] The uses of the molded article of the present disclosure are not particularly limited, and examples include bags, coating materials, tableware such as beverage containers, electric wires, cables, pipes, fibers, bottles, gasoline tanks, and other various industrial molded products.

[0182] Although the embodiments have been described above, it will be understood that various changes in form and detail can be made without departing from the spirit and scope of the claims.

Example

[0183] Next, the present disclosure will be described in more detail with reference to examples, but the present disclosure is not limited to these examples only.

[0184] In the examples and comparative examples, the following materials were used. (Antioxidant) Phenolic: Pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] Phosphoric acid-based: Tris(2,4-di-tert-butylphenyl) phosphite (Polyester resin) PLA: Polylactic acid (MFR: 3 g / 10 min, melting point: 153 °C) PBS: Polybutylene succinate (MFR: 22 g / 10 min, melting point: 114 °C) (Additive) EVOH: Ethylene-vinyl alcohol copolymer (ethylene content: 38 mol%, MFR: 1.6 g / 10 min, melting point: 172 °C) (Thermoplastic resin (B) (matrix resin)) LLDPE-1: Metallocene-catalyzed linear low-density polyethylene (MFR: 0.8 g / 10 min, melting point: 123 °C, d = 0.925, MIR = 28.1) (Thermoplastic resin (A) (carrier resin)) LLDPE-2: Metallocene-catalyzed linear low-density polyethylene (MFR: 2.0 g / 10 min, melting point: 123 °C, d = 0.925, MIR = 23.6) LLDPE-3: Ziegler-Natta catalyst type linear low density polyethylene (MFR: 2.0 g / 10 min, melting point: 123 °C, d = 0.918, MIR = 23.2)

[0185] Comparative Example 1, Examples 1 to 10 and Example 13, Comparative Example 2 First, the matrix resin, antioxidant, additive and polyester resin were melt-kneaded at a ratio shown in Tables 1 and 3 using a twin-screw extruder (TEX25αIII manufactured by Japan Steel Works, Ltd.) under the conditions of a cylinder temperature of 180 to 200 °C, a die temperature of 200 °C, and a screw rotation speed of 400 rpm to obtain a compound. Next, the processability of the obtained compound was evaluated by the following extrusion evaluation. The results are shown in Tables 1 and 3. Since none of the materials of the antioxidant, additive and polyester resin used contained fluorine, the fluorine content in the processing aid was 0% by mass.

[0186] Examples 11 to 12 First, the carrier resin, antioxidant and polyester resin were melt-kneaded at a ratio shown in Table 2 using a twin-screw extruder (TEXαIII manufactured by Japan Steel Works, Ltd.) under the conditions of a cylinder temperature of 180 to 200 °C, a die temperature of 200 °C, and a screw rotation speed of 400 rpm to obtain a masterbatch (MB). In the masterbatch, the concentration of the antioxidant was 5% by mass and the concentration of the polyester resin was 20% by mass. Next, the processability when the obtained masterbatch was dry-blended with the matrix resin at a ratio shown in Table 2 was evaluated by the following extrusion evaluation. The results are shown in Table 2. Since none of the materials of the antioxidant and polyester resin used contained fluorine, the fluorine content in the processing aid was 0% by mass.

[0187] <Extrusion Evaluation> Each material was extruded for 70 minutes under the conditions of a cylinder temperature of 170°C, a die temperature of 200°C, and a shear rate of 90 / second using a single-layer inflation molding machine (inflation die diameter: 25 mm, die gap: 0.8 mm), and evaluated according to the following items. Before each test run, linear low-density polyethylene containing 15% by mass of silica was charged into the hopper and purged for about 60 minutes. Then, after charging the same matrix resin as that used in the test and purging for about 60 minutes, it was confirmed that the initial pressure had returned, and then the next experiment was conducted. If the initial pressure had not returned, the above purging operation was repeated until the initial pressure returned, and then the next experiment was conducted. (Melt fracture (MF) disappearance time) Using only the matrix resin, extrusion was carried out until the pressure became stable with melt fracture occurring throughout, and then, when the screw became visible after that, the time was set to zero, and extrusion was carried out for 70 minutes. For examples using processing aids or masterbatches, these were charged into the hopper at the zero time point. Then, the appearance of the extruded strand at the initial stage of extrusion and the extruded strand at the completion of extrusion was confirmed by visual inspection and palpation. And the time from the zero time point described above until the MF observed at the initial stage of extrusion disappeared was measured. The shorter the time, the better. (Pressure stability) After 5 minutes had elapsed since the MF disappeared, the extrusion pressure was measured at 1-minute intervals for 20 minutes, and the standard deviation was calculated. The closer the value is to 0, the better. (Film thickness) After the start of extrusion, at the 50-minute, 60-minute, and 70-minute time points, the film was sampled for 3 minutes. For the sampled film, one measurement point was set in the TD direction of the film, and at 25°C, the film thickness was measured at 25 points (a total of 75 points) in the MD direction, and the average value, maximum value, and minimum value were calculated. Then, the thickness unevenness was calculated from the following formula. Thickness unevenness (%) = (maximum thickness (maximum value) - minimum thickness (minimum value)) / average thickness (average value) × 100

[0188]

Table 1

[0189]

Table 2

[0190]

Table 3

Claims

1. A processing aid containing a deterioration inhibitor and a polyester resin.

2. The processing aid according to Claim 1, substantially free of fluorine.

3. The processing aid according to Claim 1 or 2, wherein the deterioration inhibitor contains at least one skeleton selected from the group consisting of a phenol skeleton and a phosphoric acid skeleton.

4. The processing aid according to Claim 1 or 2, wherein the deterioration inhibitor is at least one selected from the group consisting of pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] and tris(2,4-di-tert-butylphenyl) phosphite.

5. The processing aid according to Claim 1 or 2, wherein the melting point of the polyester resin is 190 °C or lower.

6. The processing aid according to Claim 1 or 2, wherein the polyester resin is a biodegradable resin.

7. The processing aid according to Claim 1 or 2, wherein the polyester resin is polylactic acid.

8. The processing aid according to Claim 1 or 2, further containing an ethylene-vinyl alcohol copolymer.

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

10. The masterbatch according to Claim 9, wherein the thermoplastic resin (A) is a polyolefin resin.

11. The masterbatch according to Claim 9 or 10, wherein the thermoplastic resin (A) is at least one selected from the group consisting of a metallocene-catalyzed linear low-density polyethylene and a Ziegler-Natta-catalyzed linear low-density polyethylene.

12. The masterbatch according to Claim 9 or 10, wherein the mass ratio of the thermoplastic resin (A) to the processing aid (thermoplastic resin (A):processing aid) is 92:8 to 70:

30.

13. A thermoplastic resin composition containing the processing aid according to Claim 1 or 2 and / or the masterbatch according to Claim 9 or 10, and a thermoplastic resin (B).

14. The thermoplastic resin composition according to Claim 13, wherein the thermoplastic resin (B) is a polyolefin resin.

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

16. The thermoplastic resin composition according to Claim 13, wherein the content of the processing aid is 0.1 to 1% by mass.

17. A molded article using the thermoplastic resin composition according to Claim 13.

18. The molded article according to claim 17, which is tubular, film-like or sheet-like.

19. The molded article according to claim 17, wherein the thickness unevenness calculated by the following formula is 15% or less. Thickness unevenness (%) = (maximum thickness - minimum thickness) / average thickness × 100

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

21. A method for producing a masterbatch according to claim 9 or 10, comprising a mixing step and a discharging step.

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

23. A method for producing a molded article according to claim 17, comprising a molding step.

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