Processing aid, masterbatch, thermoplastic resin composition and film

Abstract

To provide a processing aid and a masterbatch which can improve workability of a thermoplastic resin, and a thermoplastic resin composition and a film using them.SOLUTION: A processing aid contains a biodegradable polymer having a melting point of 65°C or higher.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present disclosure relates to processing aids, masterbatches, thermoplastic resin compositions and films. [Background technology]

[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 if this rate is exceeded, a condition called melt fracture occurs, which causes the surface to become rough, making it impossible to obtain a good molded product.

[0003] As a method for improving the processability of thermoplastic resins, for example, Patent Documents 1 and 2 propose processing aids containing high molecular weight polyethylene glycol. However, the effect is not sufficient. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Special Publication No. 2017-538833 [Patent Document 2] US Patent Application Publication No. 2005 / 0070644 Summary of the Invention [Problem 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, and a thermoplastic resin composition and a film using the same. [Means for solving the problem]

[0006] The present disclosure (1) is a processing aid containing a biodegradable polymer having a melting point of 65°C or higher.

[0007] The present disclosure (2) is the processing aid according to the present disclosure (1), wherein the melting point of the biodegradable polymer is 190°C or lower.

[0008] The present disclosure (3) relates to the processing aid according to the present disclosure (1) or (2), in which the biodegradable polymer is an aliphatic polyester.

[0009] The present disclosure (4) relates to the processing aid according to the present disclosure (3), wherein the aliphatic polyester is at least one selected from the group consisting of polylactic acid and polybutylene succinate.

[0010] The present disclosure (5) is the processing aid according to any one of the present disclosures (1) to (4), wherein the biodegradable polymer has a melt flow rate of 0.01 to 500 g / 10 min at 190° C. under a load of 2.16 kgf, silicone, and polyamide-polyether block copolymer.

[0011] The present disclosure (6) is the processing aid according to any one of the present disclosures (1) to (5), which contains a synergist that is at least one selected from the group consisting of polyols having a melting point of 80° C. or less, polycaprolactones, silicones, and polyamide-polyether block copolymers.

[0012] The present disclosure (7) relates to the processing aid according to the present disclosure (6), wherein the polyol is polyethylene glycol and / or polyethylene oxide.

[0013] The present disclosure (8) is the processing aid according to the present disclosure (7), wherein the number average molecular weight of the polyethylene glycol is 1,000 to 50,000, the viscosity average molecular weight of the polyethylene oxide is 100,000 to 10,000,000, and the weight average molecular weight of the polycaprolactone is 2,000 to 100,000.

[0014] The present disclosure (9) is the processing aid according to any one of the present disclosures (6) to (8), in which the mass ratio of the biodegradable polymer to the synergist (biodegradable polymer:synergist) is 99.9:0.1 to 10:90.

[0015] The present disclosure (10) is the processing aid according to any one of the present disclosures (1) to (9), which contains an ethylene-vinyl alcohol copolymer.

[0016] The present disclosure (11) relates to the processing aid according to the present disclosure (10), wherein the ethylene-vinyl alcohol copolymer has a melt flow rate of 40 g / 10 min or less at 190° C. and a load of 2.16 kgf.

[0017] The present disclosure (12) relates to the processing aid according to the present disclosure (10) or (11), wherein the ethylene-vinyl alcohol copolymer has an ethylene content of 10 to 50 mol %.

[0018] The present disclosure (13) is the processing aid according to any one of the present disclosures (10) to (12), wherein the mass ratio of the biodegradable polymer to the ethylene-vinyl alcohol copolymer (biodegradable polymer:ethylene-vinyl alcohol copolymer) is 95:5 to 10:90.

[0019] The present disclosure (14) is the processing aid according to any one of the present disclosures (10) to (13), wherein the mass ratio of the biodegradable polymer to the ethylene-vinyl alcohol copolymer (biodegradable polymer:ethylene-vinyl alcohol copolymer) is 92:8 to 70:30.

[0020] The present disclosure (15) is the processing aid according to any one of the present disclosures (10) to (14), wherein the mass ratio of the biodegradable polymer, the ethylene-vinyl alcohol copolymer, and the synergist (biodegradable polymer:ethylene-vinyl alcohol copolymer:synergist) is 1 to 98:1 to 98:1 to 98.

[0021] The present disclosure (16) is the processing aid according to any one of the present disclosures (10) to (15), wherein the mass ratio of the biodegradable polymer, the ethylene-vinyl alcohol copolymer, and the synergist (biodegradable polymer:ethylene-vinyl alcohol copolymer:synergist) is 25 to 90:5 to 70:5 to 70.

[0022] The present disclosure (17) is the processing aid according to any one of the present disclosures (1) to (16), which contains a lubricant (A) that is at least one selected from the group consisting of waxes, alcohols, and surfactants.

[0023] The present disclosure (18) is the processing aid according to the present disclosure (17), wherein the mass ratio of the biodegradable polymer to the lubricant (A) (biodegradable polymer:lubricant (A)) is 99:1 to 1:99.

[0024] The present disclosure (19) is the processing aid according to the present disclosure (17) or (18), wherein the mass ratio of the biodegradable polymer to the lubricant (A) (biodegradable polymer:lubricant (A)) is 90:10 to 40:60.

[0025] The present disclosure (20) is the processing aid according to any one of the present disclosures (17) to (19), wherein a mass ratio of the biodegradable polymer, the ethylene-vinyl alcohol copolymer, and the lubricant (A) (biodegradable polymer:ethylene-vinyl alcohol copolymer:lubricant (A)) is 1 to 98:1 to 98:1 to 98.

[0026] The present disclosure (21) is the processing aid according to any one of the present disclosures (17) to (20), wherein a mass ratio of the biodegradable polymer, the ethylene-vinyl alcohol copolymer, and the lubricant (A) (biodegradable polymer:ethylene-vinyl alcohol copolymer:lubricant (A)) is 25 to 93:5 to 70:2 to 70.

[0027] The present disclosure (22) is the processing aid according to any one of the present disclosures (1) to (21), which is substantially free of fluorine.

[0028] The present disclosure (23) is a masterbatch containing the processing aid according to any one of the present disclosures (1) to (22) and a thermoplastic resin (A).

[0029] The present disclosure (24) relates to the masterbatch according to the present disclosure (23), wherein the thermoplastic resin (A) is a polyolefin resin.

[0030] The present disclosure (25) is the masterbatch according to the present disclosure (24), wherein the polyolefin resin is polyethylene.

[0031] The present disclosure (26) is the masterbatch according to any one of the present disclosures (23) to (25), wherein a mass ratio of the thermoplastic resin (A) and the processing aid (thermoplastic resin (A):processing aid) is 99:1 to 5:95.

[0032] The present disclosure (27) is the masterbatch according to any one of the present disclosures (23) to (26), which has a melt flow rate of 0.01 to 100 g / 10 min at 190° C. under a load of 2.16 kgf.

[0033] The present disclosure (28) is a thermoplastic resin composition comprising the processing aid according to any one of the present disclosures (1) to (22) and / or the masterbatch according to any one of the present disclosures (23) to (27) and a thermoplastic resin (B).

[0034] The present disclosure (29) relates to the thermoplastic resin composition according to the present disclosure (28), wherein the thermoplastic resin (B) is a polyolefin resin.

[0035] The present disclosure (30) is the thermoplastic resin composition according to the present disclosure (29), wherein the polyolefin resin is polyethylene.

[0036] The present disclosure (31) is the thermoplastic resin composition according to any one of the present disclosures (28) to (30), wherein the content of the processing aid is 0.001 to 5 mass %.

[0037] The present disclosure (32) is a film using the thermoplastic resin composition according to any one of the present disclosures (28) to (31).

[0038] The present disclosure (33) is a method for producing the processing aid according to any one of the present disclosures (1) to (22), including a mixing step and a discharging step.

[0039] The present disclosure (34) is a method for producing the masterbatch according to any one of the present disclosures (23) to (27), comprising a mixing step and a discharging step.

[0040] The present disclosure (35) is a method for producing the thermoplastic resin composition according to any one of the present disclosures (28) to (31), comprising a mixing step and a discharging step.

[0041] The present disclosure (36) is a method for producing the film according to the present disclosure (32), which includes a molding step. Effect of the Invention

[0042] According to the present disclosure, the processability of thermoplastic resins can be improved. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0043] The present disclosure will now be described in detail.

[0044] <Processing aids> The processing aid of the present disclosure comprises a biodegradable polymer with a melting point of 65° C. or higher.

[0045] In this specification, a biodegradable polymer is one that has biodegradability such that it is decomposed into low molecular weight compounds with the involvement of microorganisms in nature. For example, known biodegradable polymers include aliphatic polyesters such as polylactic acid (PLA), polybutylene succinate (PBS), polyhydroxybutyrate, polycaprolactone, polybutylene succinate / adipate, polyethylene succinate, polymalic acid, polyglycolic acid, polydioxanone, and poly(2-oxetanone); aromatic aliphatic polyesters such as polybutylene succinate / terephthalate, polybutylene adipate / terephthalate (PBAT), and polytetramethylene adipate / terephthalate; natural polymers such as starch, cellulose, chitin, chitosan, gluten, gelatin, zein, soy protein, collagen, and keratin; and polyhydroxyalkanol (PHA). Further PHAs include poly(3-hydroxybutyrate) (PHB), poly(3-hydroxybutyrate / 3-hydroxyvalerate) (PHBV), poly(3-hydroxybutyrate / 3-hydroxyhexanoate) (PHBH), poly(3-hydroxybutyrate / 4-hydroxybutyrate), and the like.

[0046] The polylactic acid is a polymer mainly composed of L-lactic acid and / or D-lactic acid, but may contain other copolymerization components other than lactic acid. Examples of other monomer units include glycol compounds such as ethylene glycol, propylene glycol, butanediol, heptanediol, hexanediol, octanediol, nonanediol, decanediol, 1,4-cyclohexanedimethanol, neopentyl glycol, glycerin, pentaerythritol, bisphenol A, polyethylene glycol, polypropylene glycol, and polytetramethylene glycol, oxalic acid, adipic acid, sebacic acid, azelaic acid, dodecanedioic acid, malonic acid, glutaric acid, cyclohexanedicarboxylic acid, terephthalic acid, Examples of the dicarboxylic acids include isophthalic acid, phthalic acid, naphthalenedicarboxylic acid, bis(p-carboxyphenyl)methane, anthracene dicarboxylic acid, 4,4'-diphenyl ether dicarboxylic acid, 5-sodium sulfoisophthalic acid, and 5-tetrabutylphosphonium isophthalic acid; hydroxycarboxylic acids such as glycolic acid, hydroxypropionic acid, hydroxybutyric acid, hydroxyvaleric acid, hydroxycaproic acid, and hydroxybenzoic acid; and lactones such as caprolactone, valerolactone, propiolactone, undecalactone, and 1,5-oxepan-2-one.

[0047] There are no particular limitations on the molecular weight and molecular weight distribution of the biodegradable polymer, so long as it can be substantially processed by extrusion molding.

[0048] The processing aid of the present disclosure was developed based on the discovery that the processability of thermoplastic resins can be significantly improved when using the above-mentioned biodegradable polymers having a melting point of 65° C. or higher. As the biodegradable polymer having a melting point of 65° C. or higher, aliphatic polyesters such as PLA and PBS are preferred, with PLA and PBS being particularly preferred.

[0049] The melting point of the biodegradable polymer may be 65° C. or higher, but is preferably 70° C. or higher, 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 even more preferably 180° C. or lower. If it is within the above range, the effect of improving processability will be better. In this specification, the melting point is the temperature corresponding to the maximum value in the heat of fusion curve when the temperature is increased at a rate of 10° C. / min using a differential scanning calorimetry (DSC) device.

[0050] The melt flow rate (MFR) of the biodegradable polymer is preferably 0.01 g / 10 min or more, more preferably 0.05 g / 10 min or more, and even more preferably 0.1 g / 10 min or more, and is preferably 500 g / 10 min or less, more preferably 300 g / 10 min or less, and even more preferably 150 g / 10 min or less. If it is within the above range, the effect of improving processability will be better. In this specification, the MFR is measured in accordance with ASTM D 1238 under conditions of 190° C. and a load of 2.16 kgf.

[0051] In the processing aid of the present disclosure, the content of the biodegradable polymer is preferably 60% by mass or more, more preferably 70% by mass or more, and even more preferably 80% by mass or more. The upper limit is not particularly limited and may be 100% by mass, but when used in combination with a synergist described below, it is preferably 99% by mass or less, more preferably 95% by mass or less.

[0052] The biodegradable polymer preferably contains 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'-.

[0053] In the above formula 1, X is X 1 and X 2 is a divalent group consisting of at least one selected from the group consisting of X 1 is a group consisting 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 is preferably an aromatic hydrocarbon group having 1 to 12 carbon atoms which may have a substituent.

[0054] 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 at each occurrence a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms).

[0055] In the above formula 1, R' is, independently in each occurrence, preferably a hydrogen atom or a hydrocarbon group having 1 to 7 carbon atoms, more preferably a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, and even more preferably a hydrogen atom or a hydrocarbon group having 1 carbon atom.

[0056] In the above formula 1, it is preferable that Y and Z are each independently a group consisting 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 at each occurrence a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms).

[0057] In the above formula 1, it is preferable that Y and Z are each independently a group consisting of at least one selected from the group consisting of a single bond, -O-, -C(=O)-, and -C(=O)O-.

[0058] In the above formula 1, R 1 , R 2 , R 3 and R 4 are each independently preferably a hydrogen atom or a hydrocarbon group having 1 to 7 carbon atoms, more preferably a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, and even more preferably a hydrogen atom or a hydrocarbon group having 1 carbon atom.

[0059] Each of n and m is independently preferably an integer of 0 to 8, more preferably an integer of 0 to 6, further preferably an integer of 0 to 4, and particularly preferably an integer of 0 to 2.

[0060] The processing aid of the present disclosure preferably contains at least one synergist selected from the group consisting of polyols having a melting point of 80° C. or less, polycaprolactone, silicone, and polyamide-polyether block copolymers, and more preferably contains at least one synergist selected from the group consisting of polyols having a melting point of 80° C. or less, and polycaprolactone. This provides a better effect of improving processability. In addition, the above polyols are preferred as synergists because of their excellent effect of improving processability.

[0061] The melting point of the polyol may be 80° C. or lower, but is preferably 75° C. or lower, more preferably 70° C. or lower, and even more preferably 68° C. or lower, and is preferably 10° C. or higher, more preferably 20° C. or higher, and even more preferably 25° C. or higher. Within the above range, the effect of improving processability is better.

[0062] The polyol may be, for example, A[(OR 11 ) x2 OR 12 ] y2 where A is usually an alkylene having one or more ether bonds, y2 is 2 or 3, and (OR 11 ) x2 is an oxyalkylene group, OR 11 is a poly(oxyalkylene) chain having multiple (x2) 11 are each independently C2-C5 alkylene, and in some embodiments, C2-C3 alkylene; R 12 is hydrogen, alkyl, aryl, arylalkenyl, alkylarylenyl, -C(O)-alkyl, -C(O)-aryl, -C(O)-arylalkenyl or -C(O)-alkylarylenyl, and -C(O)- is OR 12 is bonded to O. x2 is 10 to 230,000.

[0063] The polyol is R 11 are each -CHCH- or poly(oxypropylene), and R 11Each of these may be a homopolymer such as poly(oxyethylene), in which each is -C3H6-.

[0064] The polyols may be chains of randomly distributed oxyalkylene groups (e.g., copolymers of -OC2H4- and -OC3H6- units) or alternating blocks of repeating oxyalkylene groups (e.g., (-OC2H4-) a1 Block and (-OC3H6-) b1 It may also be a chain having a block-containing polymer, where a1+b1 is 10 to 230,000.

[0065] In some embodiments of the above polyols, A is ethylene, -CH-CH(-)-CH- (derived from glycerol), CHCHC(CH-) (derived from 1,1,1-trimethylolpropane), poly(oxypropylene), -CHCH-O-CHCH-, or -CHCH-O-CHCH-O-CHCH-; R 12 is hydrogen, methyl, butyl, phenyl, benzyl, acetyl, benzoyl or stearyl.

[0066] The polyol is a dicarboxylic acid and A[(OR 11 ) x2 OR 12 ] y2 A polyester prepared from a poly(oxyalkylene) polymer represented by the formula: 11 and x2 are as defined above, R 12 is hydrogen and y2 is 2.

[0067] The polyols may be used alone or in combination of two or more. From the viewpoint of excellent effect of improving processability, polyethylene glycol and polyethylene oxide are preferred, and polyethylene glycol is particularly preferred.

[0068] The number average molecular weight (Mn) of the polyethylene glycol is preferably 1,000 or more, more preferably 3,000 or more, and even more preferably 5,000 or more, and is preferably 50,000 or less, more preferably 45,000 or less, and even more preferably 40,000 or less. If it is within the above range, the effect of improving processability will be better. In this specification, the number average molecular weight is calculated from the hydroxyl value measured in accordance with JIS K0070.

[0069] The viscosity average molecular weight (Mv) of the polyethylene oxide is preferably 100,000 or more, more preferably 120,000 or more, and even more preferably 140,000 or more, and is preferably 10,000,000 or less, more preferably 1,600,000 or less, and even more preferably 500,000 or less. Within the above ranges, 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 of 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

[0070] The polycaprolactone may be a homopolymer of ε-caprolactone or a modified polycaprolactone, for example, one modified by coexisting 1,4-butanediol or the like during ring-opening polymerization of ε-caprolactone, or one modified at the end of the polymer with an ether or ester group or the like.

[0071] The weight average molecular weight (Mw) of the polycaprolactone is preferably 2,000 or more, more preferably 10,000 or more, and even more preferably 25,000 or more, and is preferably 100,000 or less, more preferably 95,000 or less, and even more preferably 90,000 or less. Within the above ranges, the effect of improving processability is better. In this specification, the weight average molecular weight is measured by gel permeation chromatography (GPC) in terms of polystyrene.

[0072] The melting point of the polycaprolactone is preferably 80° C. or lower, more preferably 75° C. or lower, even more preferably 70° C. or lower, even more preferably 68° C. or lower, and is preferably 10° C. or higher, more preferably 20° C. or higher, even more preferably 45° C. or higher. Within the above range, the effect of improving processability is better.

[0073] Said silicone can in principle be all organosilicon compounds known to those skilled in the art under the term silicone polymer.A suitable definition of silicone can be found in Winnacker / Kuchler: "Chemische Technik" [Chemical Technology], R.Dittmeyer, W.Keim, G.Kreysa, A.Oberholz (eds.), Volume 5: "Organische Zwischenverbindungen, Polymere" [Organic Intermediates, Polymers], Chapter: "Silicones", Wiley-VCH, Weinheim, 2005.

[0074] Silicone can be substituted or unsubstituted linear oligo- or polydiorganosiloxane, branched silicone polymer, silicone resin or crosslinked silicone polymer.Of course, mixtures of various silicone polymers can also be used.As already mentioned, silicone-containing copolymers can also be used, for example polyether functional silicones, silicones containing urea or urethane units or silicone block copolymers with organic polymers.For the purpose of better additivity, it is particularly preferred to use high molecular weight polydiorganosiloxanes, which can also contain non-silicone components, for example fillers such as finely divided silicic acid, chalk, talc and sheet silicate.

[0075] 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, a2, b2, c2, and d2 each represent 0 or an integer, and a2+b2+c2+d2 represents an integer from 5 to 15,000.

[0076] C1 to C18 hydrocarbon residues R 13Examples of are alkyl residues such as methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, for example n-hexyl, heptyl, for example n-heptyl, octyl, for example n-octyl and isooctyl, for example 2,2,4-trimethylpentyl, nonyl, for example n-nonyl, decyl, for example n-decyl, cycloalkyl, for example cyclopentyl, cyclohexyl, 4-ethylcyclohexyl and cycloheptyl, norbornyl and methylcyclohexyl. Among the alkyl residues, C1 to C6 residues, for example methyl and ethyl, in particular methyl, are preferred.

[0077] R 13 Examples of unsaturated C1 to C18 hydrocarbon residues are also alkenyl residues, such as vinyl, 2-propen-2-yl, allyl, 3-buten-1-yl, 5-hexen-1-yl, 10-undecen-1-yl, and cycloalkenyl residues (2-cyclohexenyl, 3-cyclohexenyl, cyclopentadienyl, 2-(cyclohex-3-en-1-yl)ethyl); aryl residues, such as phenyl, biphenylyl, and naphthyl; alkaryl residues, such as o-, m-, and p-tolyl, and phenethyl residues (2-phenylethyl, 1-phenylethyl), and aralkyl residues, such as benzyl. Preferred unsaturated C1 to C18 hydrocarbon residues R 13 are vinyl and phenyl residues.

[0078] residue R 13 Examples of substituted hydrocarbon residues as are halogenated hydrocarbons, such as the chloromethyl, 3-chloropropyl, 3-bromopropyl, 3,3,3-trifluoropropyl and 5,5,5,4,4,3,3-heptafluoropentyl residues, as well as the chlorophenyl, dichlorophenyl and trifluorotolyl residues.

[0079] residue R 13 is preferably bonded to the silicone polymer of formula A via a Si-C bond, but can also be bonded to the silicone polymer via an oxygen atom -O-.

[0080] R 13 has preferably 1 to 6 carbon atoms. The ethyl, phenyl, vinyl and methyl residues are particularly preferred.

[0081] 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.

[0082] Preferably, c2+d2 means <0.1×(a2+b2+c2+d2), in particular c2+d2<0.05×(a2+b2+c2+d2).

[0083] Preferably, all residues R 13 At least 50%, more preferably at least 70%, particularly preferably at least 80% represent methyl residues.

[0084] In principle, all silicone polymers corresponding to formula A can be used. However, preference is given to silicone polymers having a dynamic viscosity of more than 1000 mPa.s, preferably measured according to DIN EN ISO 3219:1994 and DIN 53019 using an Anton Paar "MCR 302" rheometer with an opening angle of 2°, a diameter of 50 mm (cone CP50-2), a measuring temperature of 25.00°C ± 0.05°C and a shear rate of 1 sec-1.

[0085] Of the silicones, silicone polymers having very high molecular weights, such as UHMW polysiloxanes (ultra-high molecular weight; as described in KJ Ryan et al., Journal of Vinyl & Additive Technology, March 2000, Vol. 6, No. 1, pp. 7-19) may be used.

[0086] The degree of polymerization of UHMW polysiloxanes ranges from >1000 to about 14000, which corresponds to a number average molecular weight between 74 kg / mol and 1000 kg / mol.

[0087] Typical UHMW polysiloxanes have a dynamic viscosity between 10 kPa.s and 50 kPa.s, preferably between 15 kPa.s and 30 kPa.s, measured with an airborne rotational rheometer according to DIN EN ISO 3219:1994 and DIN 53019, where a plate-plate system (diameter 25 mm) with a measuring gap of 0.5 mm is used. The measuring temperature is 25.00°C + / - 0.1°C. The shear rate gradient is 0.1 sec -1 The viscosity reported represents the arithmetic mean of three individual measurements carried out independently.

[0088] Of the above UHMW polysiloxanes, high molecular weight polydimethylsiloxanes having a dynamic viscosity (preferably measured by the method described above) between 1 kPa.s and 50 kPa.s, preferably between 10 and 40 kPa.s, and particularly preferably between 15 and 30 kPa.s, are particularly preferred, as they are cheap and effective.

[0089] Examples of the UHMW polysiloxane include commercially available UHMW polysiloxanes such as MULTIBASE (registered trademark) MB50-001 and MULTIBASE (registered trademark) MB50-002 manufactured by Dupont, and GENIOPLAST (registered trademark) PELLET S, GENIOPLAST (registered trademark) PELLET P Plus, GENIOPLAST (registered trademark) PE50S08, GENIOPLAST (registered trademark) PP50S12 manufactured by Wacker Asahi Kasei Silicones, and mixtures thereof, with MB50-002 and GENIOPLAST (registered trademark) PELLET S being preferred.

[0090] Silicone polymers are commercially available as ready-to-use pellets / granules or masterbatches, which can be mixed, for example, into thermoplastic granules prior to their further processing.

[0091] The 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 may also be referred to as a "polyamide / polyether block copolymer." It may also 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: [ka]

[0092] Here, PA is the polyamide block, PE is the polyether block, and p is 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: [ka]

[0093] where EG is a first unspecified end group, B is an unspecified bridging group, EG * is a second unspecified end group, and EG, B and EG * is determined by the synthesis method used to produce the PEBA copolymer, where n2 represents the length of the polyamide block, x3 represents the length of the amide moiety in the polyamide block, m1 represents the length of the poly(ether) block, y3 represents the length of the ether moiety in 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: [ka]

[0094] Here, n2 represents the length of the polyamide block, x3 represents the length of the amide moiety in the polyamide block, m1 represents the length of the poly(ether) block, y3 represents the length of the ether moiety in the poly(ether) block, p represents the length of the PEBA copolymer, and represents the total number of polyamide and polyether blocks.

[0095] The polyamide blocks in the PEBA copolymers are derived from polyamide-12 (PA-12), polyamide-11 (PA-11), polyamide-6 (PA-6), or polyamide-66 (PA-66).

[0096] 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 narrow molecular weight polymer standards using techniques known in the art.

[0097] In embodiments, the number average molecular weight Mn of the polyamide blocks 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 blocks 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 3000 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.

[0098] The PEBA copolymer has a number average molecular weight, Mn, of from 10,000 to 500,000 g / mol, including any subrange within this range and any number within this range. For example, in embodiments of the present disclosure, the PEBA copolymer has a number average molecular weight, Mn, of from 10,000 to 400,000 g / mol, or from 10,000 to 300,000 g / mol, or 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 PEBA copolymer has a number average molecular weight Mn of at least 10,000 g / mol, at least 20,000 g / mol, at least 25,000 g / mol, greater than 25,000 g / mol, at least 30,000 g / mol, greater than 30,000 g / mol, at least 35,000 g / mol, greater than 35,000 g / mol, at least 50,000 g / mol, or greater than 50,000 g / mol.

[0099] In embodiments, the weight average molecular weight Mw of the PEBA copolymer is from 25,000 to 500,000 g / mol, including any subrange 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 PEBA copolymer may be randomly distributed.

[0100] The PEBA copolymer includes a polyamide block and a polyether block, the polyamide block comprising at least 50% by weight of the copolymer. The PEBA copolymer includes a polyamide block and a polyether block, the polyether block comprising at least 50% by weight of the copolymer. Furthermore, the PEBA copolymer includes a polyamide block and a polyether block, the molar ratio of the polyamide block to the polyether block may range from 1:3 to 3:1, or from 1:2 to 2:1, or from 3:2 to 1:3, or from 2:3 to 3:1, or about 1:1.

[0101] PEBA copolymers having polyamide and polyether blocks can be prepared by the reaction of the polyamide and polyether block precursors described above. For example, a lactam, a polyether diol, and a chain-limiting diacid can be reacted together in the presence of a small amount of water to give PEBA copolymers having polyamide and polyether blocks of variable length and statistically random distribution within the block copolymer chain. The polyether blocks may be derived from poly(oxyethylene), poly(oxypropylene), or poly(tetramethylene ether) glycols, each of which may be naturally co-condensed with a polyamide block containing a carboxylic acid chain end. A chain limiter may also be present during the polycondensation reaction to provide a PEBA copolymer containing polyamide and polyether blocks randomly distributed within the block copolymer. The polyether blocks are derived from poly(oxyethylene), poly(oxypropylene), or poly(tetramethylene ether) glycols, which are first converted to polyether diamines by amination and then co-condensed with polyamide blocks containing carboxylic acid chain ends. A chain limiter may also be present during the polycondensation reaction to provide a PEBA copolymer containing polyamide and polyether blocks randomly distributed within the block copolymer. The polyether blocks can be derived from poly(oxyethylene), also known as polyethylene glycol (PEG). The polyether blocks can be derived from poly(oxypropylene), also known as polypropylene glycol (PPG). The polyether blocks may be derived from poly(tetramethylene ether) glycol (PTMG), also known as polytetramethylene oxide (PTMEO) or polytetrahydrofuran (PTHF).

[0102] The PEBA copolymer comprises i) a polyamide block selected from polyamide-12 (PA-12), polyamide-11 (PA-11), polyamide-6 (PA-6), or a mixture thereof, and ii) a polyether block selected from polyethylene glycol (PEG), polypropylene glycol (PPG), polytetrahydrofuran (PTHF), or a mixture thereof.

[0103] The PEBA copolymer comprises i) a polyamide block selected from polyamide-12 (PA-12), polyamide-11 (PA-11), polyamide-6 (PA-6), or a mixture thereof, and ii) a polyether block 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 polyethylene glycol (PEG).

[0104] The PEBA copolymer contains from 10 to 20 polyamide blocks and from 10 to 20 polyether blocks.

[0105] The PEBA copolymer contains only one type of polyamide block and one type of polyether block.

[0106] The PEBA copolymer includes i) a polyamide block which is polyamide-12 (PA-12), and ii) a polyether block which is polyethylene glycol (PEG), where the polyamide-12 block comprises about 30% to 70% by weight of the copolymer, and the polyethylene glycol block comprises about 70% to 30% by weight of the copolymer.

[0107] The PEBA copolymer includes i) a polyamide block which is polyamide-12 (PA-12), and ii) a polyether block which is polyethylene glycol (PEG), where the polyamide-12 block comprises about 40% to 60% by weight of the copolymer, and the polyethylene glycol block comprises about 60% to 40% by weight of the copolymer.

[0108] The PEBA copolymer comprises i) a polyamide block that is polyamide-12 (PA-12) and ii) a polyether block that is polyethylene glycol (PEG), where the polyamide-12 block represents about 45% by weight of the copolymer and the polyethylene glycol block represents about 55% by weight of the copolymer.

[0109] The PEBA copolymer comprises i) 10 to 20 polyamide blocks which are polyamide-12 (PA-12), and ii) 10 to 20 polyether blocks which are polyethylene glycol (PEG).

[0110] The PEBA copolymer comprises i) a polyamide block which is polyamide-12 (PA-12), and ii) a polyether block which is polyethylene glycol (PEG), and has a number average molecular weight Mn of about 25,000 to about 75,000 g / mol.

[0111] The PEBA copolymer comprises i) a polyamide block which is polyamide-12 (PA-12) and ii) a polyether block which is polyethylene glycol (PEG) and has a number average molecular weight Mn of about 50,000 to about 75,000 g / mol.The PEBA copolymer comprises i) a polyamide block which is polyamide-12 (PA-12) and ii) a polyether block which is polyethylene glycol (PEG) and has a number average molecular weight Mn of about 66,100 g / mol.

[0112] The PEBA copolymer includes 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.

[0113] The PEBA copolymer includes 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.

[0114] The PEBA copolymer comprises i) a polyamide block which is polyamide-12 (PA-12) and ii) a polyether block which is polyethylene glycol (PEG), and has a weight average molecular weight Mw of about 134,000 g / mol.

[0115] 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 which is polyamide-6 (PA-6) and ii) a polyether block which is polyethylene glycol (PEG), where the polyamide-6 block represents about 30% to 60% by weight of the copolymer and the polyethylene glycol block represents about 70% to 40% by weight of the copolymer.

[0116] The PEBA copolymer comprises 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 about 50% to 35% by weight of the copolymer and the polyethylene glycol block represents about 50% to 65% by weight of the copolymer.

[0117] The PEBA copolymer comprises i) 10 to 20 polyamide blocks which are polyamide-6 (PA-6), and ii) 10 to 20 polyether blocks which are polyethylene glycol (PEG).

[0118] The PEBA copolymer includes i) a polyamide block that is polyamide-11 (PA-11), and ii) a polyether block that is polyethylene glycol (PEG). In one embodiment of the present disclosure, the PEBA copolymer includes i) a polyamide block that is polyamide-12 (PA-12), and ii) a polyether block that is polytetrahydrofuran (PTHF).

[0119] The PEBA copolymer comprises i) a polyamide block which is polyamide-12 (PA-12), and ii) a polyether block which is polytetrahydrofuran (PTHF), wherein the polyamide-12 block represents about 75% to 10% by weight of the copolymer and the polytetrahydrofuran block represents about 25% to 90% by weight of the copolymer.

[0120] The PEBA copolymer comprises i) a polyamide block which is polyamide-12 (PA-12), and ii) a polyether block which is polytetrahydrofuran (PTHF), wherein the polyamide-12 block represents about 80% to 60% by weight of the copolymer and the polytetrahydrofuran block represents about 20% to 40% by weight of the copolymer.

[0121] The PEBA copolymer comprises i) a polyamide block which is polyamide-12 (PA-12), and ii) a polyether block which is polytetrahydrofuran (PTHF), wherein the polyamide-12 block represents about 40% to 60% by weight of the copolymer and the polytetrahydrofuran block represents about 60% to 40% by weight of the copolymer.

[0122] The PEBA copolymer comprises i) a polyamide block which is polyamide-12 (PA-12), and ii) a polyether block which is polytetrahydrofuran (PTHF), where the polyamide-12 block represents about 30% to 10% by weight of the copolymer and the polytetrahydrofuran block represents about 70% to 90% by weight of the copolymer. The PEBA copolymer comprises i) 10 to 20 polyamide blocks which are polyamide-12 (PA-12), and ii) 10 to 20 polyether blocks which are polytetrahydrofuran (PTHF).

[0123] The PEBA copolymer comprises i) a polyamide block which is polyamide-12 (PA-12) and ii) a polyether block which is polytetrahydrofuran (PTHF), and has a number average molecular weight Mn of about 25,000 to about 75,000 g / mol. The PEBA copolymer comprises i) a polyamide block that is polyamide-12 (PA-12) and ii) a polyether block that 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 comprises i) a polyamide block that is polyamide-12 (PA-12) and ii) a polyether block that is polytetrahydrofuran (PTHF), and has a number average molecular weight Mn of about 50,000 g / mol.

[0124] The PEBA copolymer includes i) a polyamide block that is polyamide-6 (PA-6), and ii) a polyether block that is polytetrahydrofuran (PTHF). The PEBA copolymer includes i) a polyamide block that is polyamide-11 (PA-11), and ii) a polyether block that is polytetrahydrofuran (PTHF). The PEBA copolymer is a commercially available elastomer sold under the trade name PEBAX®.

[0125] The PEBA copolymer is a commercially available elastomer selected from the group consisting of: PEBAX 2533 SA 01, PEBAX 2533 SA 01 MED, PEBAX 2533 SD 02, PEBAX 3533 SA 01, PEBAX 3533 SA 01 MED, PEBAX 3533 SP01, PEBAX 4011, PEBAX 4033 SA 01, PEBAX 4033 SA 01 MED, PEBAX 4033 SP01, PEBAX 4533 SA 01, PEBAX 4533 SA 01 MED, PEBAX 4533 SP01, PEBAX 5513 SA 01, PEBAX 5513 SP01, PEBAX 5533 SA 01, PEBAX 5533 SA 01 MED, PEBAX 5533 SN 70 BLACK, PEBAX 5533 SP01, PEBAX SA 01, PEBAX 6333 SA 01 MED, PEBAX SP01, PEBAX 6333 SP01, PEBAX 6333 SA 01, PEBAX, PEBAX 3533 SA 01, PEBAX 3533 SA 01 MED, PEBAX 3533 SP01, PEBAX 4011 SA 01, PEBAX 4033 SA 01 MED, PEBAX 4033 SP01, PEBAX 4033 SA 01 MED, PEBAX Clear 2533, PEBAX ES 2533 UV, PEBAX MH 2533, PEBAX MH2030, PEBAX MV 5513 SA 01, PEBAX MV 5513 Examples include SA 01 MED, PEBAX MV 5533 SP01, PEBAX MV 5533, PEBAX MV 5533 SP01, PEBAX RNEW® 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 PEBA copolymer is a commercially available elastomer sold under the trade name VESTAMID® or VESTAMID E.

[0126] The PEBA copolymer is a commercially available elastomer selected from the group consisting of VESTAMID D, VESTAMID DX, VESTAMID E, VESTAMID EX, VESTAMID Care, VESTAMID Care ML, VESTAMID Care ME, VESTAMID Care ME-B, VESTAMID L, VESTAMID LX, VESTAMID NRG, VESTAMID Terra, VESTAMID X, and mixtures thereof. Among these, Pebax MV1072 is preferred.

[0127] The PEBA copolymers can be used in the form of a semi-solid or viscous liquid, or as a powder, pellets, or granules.

[0128] In the processing aid of the present disclosure, the content of the synergist is preferably 0.1 mass% or more, more preferably 0.5 mass% or more, even more preferably 1 mass% or more, and is preferably 40 mass% or less, more preferably 30 mass% or less, even more preferably 20 mass% or less.

[0129] In the processing aid of the present disclosure, the mass ratio of the biodegradable polymer and the synergist (biodegradable polymer: synergist) is preferably 99.9:0.1 to 10:90. The mass ratio is more preferably 99.5:0.5 to 30:70, further preferably 99:1 to 50:50, and particularly preferably 98:2 to 60:40. The mass ratio may be 99.5:0.5 to 70:30, 99:1 to 85:15, or 98:2 to 92:8. When the processing aid of the present disclosure does not include an ethylene-vinyl alcohol copolymer, the mass ratio may be 99.9:0.1 to 10:90, 99.5:0.5 to 70:30, 99:1 to 85:15, or 98:2 to 92:8.

[0130] In the processing aid of the present disclosure, the total content of the biodegradable polymer and the synergist is preferably 70% by mass or more, more preferably 80% by mass or more, even more preferably 85% by mass or more, and particularly preferably 90% by mass or more. The total content of the biodegradable polymer and the synergist may be 80% by mass or more, 90% by mass or more, 95% by mass or more, or 100% by mass.

[0131] The processing aid of the present disclosure may contain ingredients other than the biodegradable polymer and the synergist.

[0132] The processing aid of the present disclosure preferably contains an ethylene-vinyl alcohol copolymer, which provides a better effect of improving processability.

[0133] The melt flow rate (MFR) of the ethylene-vinyl alcohol copolymer is preferably 0.001 g / 10 min or more, more preferably 0.1 g / 10 min or more, even more preferably 0.5 g / 10 min or more, and is preferably 40 g / 10 min or less, more preferably 20 g / 10 min or less, even more preferably 10 g / 10 min or less. If it is within the above range, the effect of improving processability is better.

[0134] The ethylene content of the ethylene-vinyl alcohol copolymer is preferably 5 mol% or more, more preferably 10 mol% or more, and even more preferably 15 mol% or more, and is preferably 50 mol% or less, 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) methods.

[0135] The ethylene-vinyl alcohol copolymer is preferably one obtained by saponifying an ethylene-vinyl ester copolymer, and among these, one obtained by saponifying an ethylene-vinyl acetate copolymer is particularly preferred.

[0136] The saponification degree of the ethylene-vinyl alcohol copolymer is preferably 80 to 100 mol %.

[0137] When copolymerizing ethylene and vinyl acetate, other fatty acid vinyl esters (vinyl propionate, vinyl pivalate, etc.) can also be used in combination. The ethylene-vinyl alcohol copolymer can also contain 0.0002 to 0.2 mol% of a vinylsilane-based compound as a copolymerization component. Examples of the vinylsilane-based compound include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri(β-methoxy-ethoxy)silane, and γ-methacryloxypropylmethoxysilane. Among these, vinyltrimethoxysilane and vinyltriethoxysilane are preferably used.

[0138] When ethylene and vinyl acetate are copolymerized, it is also possible to coexist in small amounts with monomers other than the above-mentioned fatty acid vinyl 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; nitriles such as acrylonitrile and methacrylonitrile; amides such as acrylamide and methacrylamide; olefin sulfonic acids such as ethylene sulfonic acid, allyl sulfonic acid, and methallyl sulfonic acid, or their salts; alkyl vinyl ethers, vinyl ketones, N-vinylpyrrolidone, vinyl chloride, vinylidene chloride, and the like.

[0139] In the ethylene-vinyl alcohol copolymer, the content of polymerized units based on monomers other than ethylene and vinyl alcohol is preferably 10 mol % or less, more preferably 5 mol % or less, and even more preferably 1 mol % or less. The lower limit is not particularly limited, and may be 0 mass %. In this specification, the content of polymerized units based on monomers other than ethylene and vinyl alcohol is determined by a nuclear magnetic resonance (NMR) method.

[0140] In the processing aid of the present disclosure, the content of the ethylene-vinyl alcohol copolymer is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, even more preferably 1% by mass or more, and is preferably 90% by mass or less, more preferably 70% by mass or less, even more preferably 50% by mass or less.

[0141] In the processing aid of the present disclosure, the mass ratio of the biodegradable polymer to the ethylene-vinyl alcohol copolymer (biodegradable polymer:ethylene-vinyl alcohol copolymer) is preferably 99:3 to 50:50. The mass ratio is more preferably 95:5 to 60:40, further preferably 92:8 to 70:30, and particularly preferably 90:10 to 75:25. The mass ratio may be 95:5 to 10:90, 90:10 to 75:25, 80:20 to 60:40, or 60:40 to 40:60.

[0142] In the processing aid of the present disclosure, the mass ratio of the biodegradable polymer, the ethylene-vinyl alcohol copolymer, and the synergist (biodegradable polymer:ethylene-vinyl alcohol copolymer:synergist) is preferably 1-98:1-98:1-98, more preferably 25-90:5-70:5-70, and most preferably 56-88:7-39:5-37.

[0143] In the processing aid of the present disclosure, the total content of the biodegradable polymer and the ethylene-vinyl alcohol copolymer is preferably 10% by mass or more, more preferably 50% by mass or more, and even more preferably 70% by mass or more. The total content of the biodegradable polymer and the ethylene-vinyl alcohol copolymer may be 80% by mass or more, 90% by mass or more, 95% by mass or more, or even 100% by mass.

[0144] The processing aid of the present disclosure preferably comprises a lubricant (A).

[0145] The lubricant (A) is an additive that reduces friction and improves slipperiness, and examples thereof include waxes, alcohols, surfactants, etc. These may be used alone or in combination of two or more. The lubricant (A) is preferably at least one selected from the group consisting of waxes, alcohols, and surfactants.

[0146] Examples of the waxes include pure hydrocarbon waxes such as liquid paraffin, natural paraffin, micro wax, synthetic paraffin, polyethylene wax, and polyethylene / polypropylene wax; fatty acid waxes such as higher fatty acids and oxy fatty acids; fatty acid amide waxes such as fatty acid amides and bisfatty acid amides; and fatty acid ester waxes such as lower alcohol esters of fatty acids, polyhydric alcohol esters of fatty acids such as glycerides, polyglycol esters of fatty acids, and fatty alcohol esters of fatty acids (ester waxes). Among these, pure hydrocarbon waxes or fatty acid ester waxes are preferred. As pure hydrocarbon waxes, polyethylene wax and polyethylene / polypropylene wax are preferred, and as fatty acid ester waxes, adipic acid esters or glycerin fatty acid esters are preferred.

[0147] Examples of fatty acid ester waxes include phthalates, dimethyl and diethyl succinates and related esters, glycerol monoacetate, glycerol diacetate, glycerol triacetate, glycerol monoacid esters, citrate esters, adipates, stearates, oleates, etc. These may be used alone or in combination of two or more kinds.

[0148] Examples of the adipic acid ester include adipic acid diester. Specifically, dimethyl adipate, dibutyl adipate, bis[2-(2-methoxyethoxy)ethyl]adipate, bis(butyl diglycol)adipate, bis(methyl diglycol)adipate, benzyl[2-(2-methoxyethoxy)ethyl]adipate, di-n-butyl adipate, dioctyl adipate, methyl diglycol butyl diglycol adipate, benzyl methyl glycol adipate, benzyl butyl diglycol adipate, diisononyl phthalate, etc. These may be used alone or in combination of two or more. Among them, diisononyl phthalate or dioctyl adipate is preferred.

[0149] Glycerin fatty acid esters include glycerin monostearate, glycerin monobehenate, glycerin mono 12-hydroxystearate, glycerin monooleate, glycerin monocaprylate, glycerin monocaprate, glycerin monolaurate, glycerin diacetomonolaurate, succinic acid fatty acid monoglyceride, and citric acid fatty acid. Examples of the monoglyceride include monoglyceride diacetyl tartaric acid, diglycerol laurate, diglycerol stearate, diglycerol oleate, diglycerol monolaurate, diglycerol monomyristate, diglycerol monostearate, diglycerol monooleate, tetraglycerol stearate, decaglycerol laurate, decaglycerol stearate, decaglycerol oleate, polyglycerol polyricinoleate, propylene glycol monolaurate, propylene glycol monopalmitate, propylene glycol monostearate, propylene glycol monooleate, and propylene glycol monobehenate. These may be used alone or in combination of two or more. Among these, glycerol diacetomonolaurate or decaglycerol stearate is preferred.

[0150] Examples of the alcohols include fatty alcohols such as higher alcohols; and polyhydric alcohols such as polyglycols and polyglycerols.

[0151] Examples of fatty alcohols include lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol, behenyl alcohol, etc. These may be used alone or in combination of two or more kinds.

[0152] Examples of the surfactant include anionic surfactants such as metal soaps and ammonium salts; cationic surfactants such as alkylamine salts and quaternary ammonium salts; nonionic surfactants such as ester type, ether type, ester / ether type, and amide type; and amphoteric surfactants such as aminocarboxylates, alkylbetaines, and alkylimidazoline derivatives. Among these, anionic surface active agents or nonionic surfactants are preferred. As anionic surfactants, metal soaps are preferred, specifically, carboxylates, sulfates, sulfonates, and phosphate salts are preferred. As nonionic surfactants, ester / ether type is preferred, specifically, sugar type surfactants are preferred.

[0153] Examples of the metal soap include fatty acid salts, polysulfonates, polycarboxylates, alkyl sulfates, alkylaryl sulfonates, alkylnaphthalenesulfonates, dialkylsulfonates, dialkylsulfosuccinates, alkyl phosphates, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkylaryl ether sulfates, and polyoxyethylene alkyl phosphate sulfonates, and more specifically, examples of the metal soap include sodium dodecylbenzenesulfonate, sodium lauryl sulfate, sodium polyoxyethylene lauryl ether sulfate, and polyoxyethylene nonylphenyl ether sulfate. These may be used alone or in combination of two or more kinds.

[0154] The metal soap is preferably a compound represented by the following general formula (1). (R 5 COO) n1 M 1 (1) (In the above general formula (1), R 5 is a hydrogen atom or an alkyl group having 1 to 21 carbon atoms, n1 is an integer ranging from 1 to 4, and M 1 is lithium, sodium, potassium, rubidium, cesium, boron, magnesium, aluminum, calcium, manganese, iron, cobalt, nickel, tin, antimony, copper, silver, zinc, molybdenum, vanadium, strontium, zirconium, barium, bismuth, lead, gold, platinum, or rare earth.

[0155] In the general formula (1), when n1 is an integer of 2 or more, a plurality of R 5 may be the same as or different from each other.

[0156] R 5 The alkyl group having 1 to 21 carbon atoms may be a straight-chain alkyl group, a branched alkyl group, or may contain an alicyclic structure.

[0157] R 5 The alkyl group having 1 to 21 carbon atoms is R 5 It corresponds to a carboxylic acid residue obtained by removing a carboxyl group (COOH) from a carboxylic acid having 1 to 22 carbon atoms, represented by COOH. Examples of the carboxylic acid residue include acetic acid residue, propionic acid residue, butanoic acid residue, pentanoic acid residue, acrylic acid residue, methacrylic acid residue, octylic acid residue (2-ethylhexanoic acid residue), neodecanoic acid residue, naphthenic acid residue, isononanoic acid residue, tung oil acid residue, tall oil fatty acid residue, coconut oil fatty acid residue, soybean oil fatty acid residue, linseed oil fatty acid residue, safflower oil fatty acid residue, dehydrated castor oil fatty acid residue, tung oil fatty acid residue, lauric acid residue, myristic acid residue, palmitic acid residue, stearic acid residue, isostearic acid residue, oleic acid residue, and 12-hydroxystearic acid residue.

[0158] R 5From the viewpoint of improving processability, the alkyl group having 1 to 21 carbon atoms is preferably an alkyl group having 12 to 21 carbon atoms, more preferably an alkyl group having 16 to 21 carbon atoms, and even more preferably a stearic acid residue or a 12-hydroxystearic acid residue.

[0159] M 1 is lithium, sodium, potassium, rubidium, cesium, boron, magnesium, aluminum, calcium, manganese, iron, cobalt, nickel, tin, antimony, copper, silver, zinc, molybdenum, vanadium, strontium, zirconium, barium, bismuth, lead, gold, or platinum.

[0160] n1 is M 1 This is a value determined by the ionic valence of the metal atom, for example, M 1 If is boron, n1 is 3, and M 1 If is cobalt, then n1 is 2.

[0161] The metal soap also includes a form of a fatty acid metal borate. The fatty acid metal borate is, for example, a compound represented by the following general formula (2). (R 6 COO-M 2 -O)3B (2) (In the general formula (2), R 6 is a hydrogen atom or an alkyl group having 1 to 21 carbon atoms, and M 2 is boron, magnesium, aluminum, calcium, manganese, iron, cobalt, nickel, tin, antimony, copper, zinc, molybdenum, vanadium, strontium, zirconium, barium, bismuth, lead, gold, or platinum.

[0162] In the general formula (2), R 6 The alkyl group having 1 to 21 carbon atoms is R 5 Similarly, in the general formula (2), M 2 The metal is M in the general formula (1). 1 is the same as the metal.

[0163] The above metal soap may be used alone, or two or more metal soaps having mutually different structures may be used.

[0164] Specific examples of the metal soap include metal salts of stearic acid, metal salts of hydroxystearic acid, etc. The metal soap is preferably at least one selected from the group consisting of metal salts of stearic acid and metal salts of hydroxystearic acid, and more preferably at least one selected from the group consisting of zinc stearate, magnesium hydroxystearate, and calcium stearate. Examples of the metal constituting the metal salt include zinc, magnesium, calcium, etc., and the metal is preferably at least one selected from the group consisting of zinc, magnesium, and calcium, and more preferably at least one selected from the group consisting of zinc and magnesium. The metal soap can be produced by a known method, and a commercially available product may be used.

[0165] The ammonium salt-based anionic surfactant may be a fatty acid ammonium salt, etc. For example, ammonium lauryl sulfate, ammonium polyoxyethylene lauryl ether sulfate, etc. The anionic surfactant may be one type or two or more types.

[0166] Examples of cationic surfactants include alkylamine salts and quaternary ammonium salts, and more specifically, examples of cationic surfactants include stearylamine acetate, trimethyl coconut ammonium chloride, trimethyl beef tallow ammonium chloride, dimethyldioleyl ammonium chloride, methyl oleyl diethanol chloride, tetramethyl ammonium chloride, lauryl pyridinium chloride, lauryl pyridinium bromide, lauryl pyridinium disulfate, cetyl trimethyl ammonium chloride, cetyl pyridinium bromide, 4-alkyl mercaptopyridine, poly(vinylpyridine)-dodecyl bromide, and dodecyl benzyl triethyl ammonium chloride. The cationic surfactant may be one type only, or two or more types.

[0167] Examples of amphoteric surfactants include aminocarboxylates, alkyl betaines, and alkyl imidazoline derivatives, and more specifically, lauric acid amidopropyl betaine. The amphoteric surfactant may be one type or two or more types.

[0168] Examples of the ether type nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyalkylene derivatives, polyoxyethylene phenyl ethers, and alkyl allyl ethers, and specific examples thereof include polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, and polyoxyethylene octylphenyl ether. Examples of the ester / ether type nonionic surfactants include sugar type surfactants, specifically sorbitan fatty acid esters, sorbitol, and polyoxyethylene sorbitan fatty acid esters. The nonionic surfactant may be used alone or in combination of two or more kinds.

[0169] Examples of the sugar-type surfactant include sucrose fatty acid esters, sorbitan acid esters, polysorbates, and the like. Specific examples of the sugar-type surfactant include sorbitol fatty acid esters such as sorbitol monolaurate, sorbitol monostearate, sorbitol monooleate, sorbitol trioleate, sorbitol tristearate, and sorbitol monoisostearate; sorbitan isostearate, sorbitan oleate, sorbitan caprylate, sorbitan dioleate, sorbitan distearate, sorbitan stearate, sorbitan sesquiisostearate, sorbitan sesquioleate, ... Sorbitan fatty acid esters such as sorbitan caprylate, sorbitan sesquistearate, sorbitan triisostearate, sorbitan trioleate, sorbitan tristearate, sorbitan palmitate, sorbitan coconutate, sorbitan laurate, and sorbitan olidate; sucrose acetate isobutyrate, sucrose octaacetate, sucrose oleate, sucrose distearate, sucrose dilaurate, sucrose stearate, sucrose tetraisostearate, tetra ... Sucrose hydroxystearate, sucrose tristearate, sucrose tribehenate, sucrose trilaurate, sucrose tetrastearate triacetate, sucrose palmitate, sucrose hexaerucate, sucrose hexapalmitate, sucrose pentaerucate, sucrose pentahydroxystearate, sucrose polyoleate, sucrose polystearate, polysucrose soyate, polysucrose palmate, sucrose polybehenate, polylaurin Examples of the sucrose fatty acid ester include sucrose fatty acid esters such as sucrose acid, sucrose polylinoleate, polycottonseed fatty acid sucrose, sucrose myristate, coconut fatty acid sucrose, sucrose laurate, sucrose ricinoleate, sucrose benzoate, sucrose acetate distearate, and sucrose acetate stearate; and alkyl glucosides such as coconut oil fatty acid glucoside, lauryl glucoside, decyl glucoside, myristyl glucoside, palmityl glucoside, stearyl glucoside, and coco glucoside. These may be used alone or in combination of two or more.

[0170] As the sugar-type surfactant, sorbitan esters containing a non-polar carboxylic acid (lipophilic group) bonded to a polar sorbitan group (hydrophilic group) by an ester bond are preferred. Further, polyoxyethylene derivatives of sorbitan esters and a plurality of polyoxyethylene oligomers chemically substituted on the sorbitan group are also preferred.

[0171] These polyoxyethylene derivatives of sorbitan esters are called polysorbates. Specifically, a polyoxyethylene derivative of sorbitan ester (also referred to as polysorbate) has the formula (I):

Chemical formula

[0172] Here, one of R 7 ~R 10 is a linear fatty acid moiety, and the other three of R 7 ~R 10 are each hydrogen. Also, w1, x1, y1, z1 are integers such that 10 < w1 + x1 + y1 + z1 < 40. Preferably 15 < w1 + x1 + y1 + z1 < 25, and more preferably w1 + x1 + y1 + z1 = 20. Also, the linear fatty acid moiety is preferably (C=O)(CH2) a CH3. The formula being (C=O)(CH2) b (CH)=(CH)(CH2) c CH3, the fatty acid moiety may alternatively contain a double bond along a hydrocarbon chain (i.e., may contain mono-unsaturation). Here, a is an integer from 10 to 25, preferably an integer from 12 to 18. Further, the linear fatty acid may contain an unsaturated bond. Also, b + c is an integer between 8 and 23, preferably an integer from 10 to 18. The number of unsaturated bonds may contain two or more unsaturations in the hydrocarbon chain, but the unsaturation is preferably 4 or less, more preferably 3 or less, and particularly preferably maintained at 0, 1, or 2.

[0173] Specific examples of polysorbates include polysorbate 20 (polyoxyethylene (20) sorbitan monolaurate), polysorbate 40 (polyoxyethylene (20) sorbitan monopalmitate), polysorbate 60 (polyoxyethylene (20) sorbitan monostearate), and polysorbate 80 (polyoxyethylene (20) sorbitan monooleate).

[0174] The 20, 40, 60, and 80 following "polysorbate" indicate the fatty acid moiety (the "lipophilic group" of the molecule) that is attached to the polyoxyethylene sorbitan portion (the "hydrophilic group" of the molecule), with 20 being monolaurate, 40 being monopalmitic acid, 60 being monostearic acid, and 80 being monooleic acid (an example of a monounsaturated fatty acid moiety).

[0175] The name "Polysorbate#" refers to the addition of 20 oxyethylene moieties [-(CH2CH2O)-] to the sorbate.

[0176] In certain embodiments, the glycosurfactant can be or include one or more of polysorbate 20, polysorbate 40, polysorbate 60, and / or polysorbate 80. For example, the surfactant can be polysorbate 60 or can include other polysorbates.

[0177] Moreover, instead of the above-mentioned polysorbates, surfactants which are variants of the above-mentioned specific polysorbates may be used. For example, with reference to Formula I, R 7 ~R 10 Two, three or all of the straight chain fatty acid moieties (R 7 ~R 10 The remainder, if any, may be hydrogen. An example of this compound is R 7 ~R 10 The three fatty acid moieties are stearic acid and R 7 ~R 10The other one includes polyoxyethylene sorbitan trisitolate, in which hydrogen is used.

[0178] In the processing aid of the present disclosure, the content of the lubricant (A) is preferably 1 mass% or more, more preferably 2 mass% or more, even more preferably 4 mass% or more, and preferably 99 mass% or less, more preferably 60 mass% or less, even more preferably 40 mass% or less.

[0179] In the processing aid of the present disclosure, the mass ratio of the biodegradable polymer to the lubricant (A) (biodegradable polymer:lubricant (A) is preferably 99:1 to 1:99, more preferably 90:10 to 40:60, and most preferably 80:20 to 60:40.

[0180] In the processing aid of the present disclosure, the mass ratio of the biodegradable polymer, the ethylene-vinyl alcohol copolymer, and the lubricant (A) (biodegradable polymer:ethylene-vinyl alcohol copolymer:lubricant (A) is preferably 1-98:1-98:1-98, more preferably 25-93:5-70:2-70, and most preferably 72-86:10-24:4-18.

[0181] A suitable combination of the biodegradable polymer, the ethylene-vinyl alcohol copolymer, and the lubricant (A) is a combination of the biodegradable polymer polylactic acid and / or polybutylene succinate, the ethylene-vinyl alcohol copolymer, and at least one selected from the group consisting of zinc stearate, magnesium hydroxystearate, and calcium stearate, as the lubricant (A). However, combinations other than those mentioned above may also be used.

[0182] The processing aid of the present disclosure preferably includes an anti-degradant.

[0183] 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 suitably used.

[0184] 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, even more preferably 3 or more, particularly preferably 4 or more, and is preferably 100 or less, more preferably 10 or less, and even more preferably 6 or less.

[0185] Specific examples of the deterioration inhibitor having a phenol skeleton include 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 cresol, 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 and other compounds having one phenol skeleton (monocyclic phenol compounds); 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), Compounds having two phenol skeletons (bicyclic phenol compounds), such as 3,6-dioxaoctamethylene bis[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], and 2,2'-thiodiethylene bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate];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- Compounds having three phenol skeletons such as tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene (3-ring phenol compounds); compounds having four phenol skeletons such as tetrakis[methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]methane and pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (4-ring phenol compounds) are preferred. Among these, 4-ring phenol compounds are preferred, with tetrakis[methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]methane and pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] being more preferred, and pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] being even more preferred.;

[0186] The phosphate skeleton has a structure in which one P (phosphorus atom) is bonded to one to four O (oxygen atoms). Among them, a structure in which three O (oxygen atoms) are bonded to one P (phosphorus atom) is preferred.

[0187] When the above-mentioned deterioration inhibitor has a phosphate skeleton, the number is not particularly limited, but is preferably 1 or more, more preferably 2 or more, even more preferably 3 or more, and is preferably 100 or less, more preferably 10 or less, even more preferably 6 or less.

[0188] Specific examples of the deterioration inhibitor having a phosphate skeleton include: [ka] (However, R 1 is selected from the group consisting of linear or branched alkyl groups having 1 to 16 carbon atoms and aryl groups; R 1 may be the same or different), and P(OR 1 )3 (where R 1 is selected from the group consisting of linear or branched alkyl groups having 4 to 32 carbon atoms), more specific examples thereof include trilauryl phosphite, triisodecyl phosphite, tridecyl phosphite, trihexadecyl phosphite, trioctadecyl phosphite, tribehenyl phosphite, triaraquidyl phosphite, triceryl phosphite, trioleyl phosphite, tris(2-ethylhexyl) phosphite, diphosphates such as monostearyl phosphite (or its tautomer, monostearyl phosphonate) and distearyl phosphite (distearyl phosphonate) and high molecular weight homologues, partially esterified phosphonic acid compounds, and alkali salts, alkaline earth salts, aluminum salts or zinc salts thereof.

[0189] Examples of diphosphites include tetraethyl diphosphite and tetrapropyl diphosphite. An example of a triphosphite is the P,P'-bis(2-hydroxyethyl) ester of triphosphoric acid.

[0190] Oligophosphites and polyphosphites (oligomeric and polymeric phosphites) are described, for example, in International Publication No. WO 2011 / 102861, International Publication No. WO 2014 / 20519, International Publication No. WO 2020 / 123986, etc. Compounds described therein can also be used. Examples include the following compounds.

[0191] [ka]

[0192] Also included are phosphates, diphosphates, metaphosphates, polyphosphates derived from the aforementioned phosphites, such as, for example, trilauryl phosphate, triisodecyl phosphate, tridecyl phosphate, trihexadecyl phosphate, trioctadecyl phosphate, tribehenyl phosphate, triaraquidyl phosphate, triceryl phosphate, trioleyl phosphate, and the following structures and salts derived therefrom, as well as mixtures of at least two phosphates selected from the group consisting of monoalkyl phosphates, dialkyl phosphates, and trialkyl phosphates.

[0193] [ka]

[0194] In the case of the aforementioned phosphite derivatives, the aforementioned phosphates, diphosphates, metaphosphates, and polyphosphates, the phosphorus atom is present in the +V oxidation state rather than the +III oxidation state as in the phosphites.

[0195] The deterioration inhibitor having a phosphoric acid skeleton is preferably a phosphite. Examples of the phosphite include the following compounds.

[0196] [ka]

[0197] [ka]

[0198] [ka]

[0199] A particularly suitable phosphite is also tris(2,4-di-tert-butylphenyl) phosphite.

[0200] Specific examples of the 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).

[0201] The deterioration inhibitor may have only either a phenol skeleton or a phosphate skeleton, or may have both a phenol skeleton and a phosphate skeleton, but is preferably one having only either a phenol skeleton or a phosphate skeleton.

[0202] It is preferable to use the deterioration inhibitor having only a phenol skeleton (phenol-based deterioration inhibitor) in combination with the deterioration inhibitor having only a phosphoric acid skeleton (phosphoric acid-based deterioration inhibitor), which improves pressure stability during extrusion.

[0203] When a phenol-based deterioration inhibitor and a phosphoric acid-based deterioration inhibitor are used in combination as the deterioration inhibitor, the mass ratio thereof (phenol-based deterioration inhibitor: phosphoric acid-based deterioration inhibitor) is preferably 20:80 to 80:20. The mass ratio is more preferably 30:70 to 70:30, further preferably 40:60 to 60:40, and particularly preferably 50:50.

[0204] 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 30% by mass or more, even more preferably 40% by mass or more, and preferably 80% by mass or less, more preferably 70% by mass or less, even more preferably 60% by mass or less.

[0205] 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 more preferable that the processing aid of the present disclosure is free of fluorine (the fluorine content is 0 mass %).

[0206] The processing aid of the present disclosure may be obtained, for example, by carrying out a mixing step of feeding the biodegradable polymer into a mixer or the like and mixing it, and a discharging step of discharging the mixture from the mixer or the like. The present disclosure also relates to a method for producing the above-mentioned processing aid, which includes the mixing step and the discharging step.

[0207] The method of the mixing step is not particularly limited, and may be mixing (kneading) with or without shear force. Among them, in order to effectively exert the above-mentioned moldability, kneading is preferred, and melt kneading is more preferred. In the case of melt-kneading, the components may be melted in the mixing step or before the mixing step.

[0208] In the above-mentioned manufacturing method, after the discharging step, a molding step of shaping the discharged material by a molding machine or the like may be carried out. The method for the molding step is not particularly limited, and examples thereof include extrusion molding, injection molding, blow molding, and the like. Among these, extrusion molding is preferred in order to effectively exert the above-mentioned moldability.

[0209] An extruder is used for the extrusion molding. Examples of the extruder include a single screw extruder, a twin screw extruder, and a tandem extruder. The 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.

[0210] The various conditions related to the above molding are not particularly limited, and can be appropriately set depending on the composition and amount of the composition, the shape and size of the desired molded product, etc. The shape of the processing aid of the present disclosure is not particularly limited, and may be powder, granules, pellets, etc., but pellets are preferred because they are easy to handle and mold.

[0211] The processing aids of the present disclosure are particularly useful as processing aids for thermoplastic resins, particularly polyolefin resins.

[0212] <Master batch> The masterbatch of the present disclosure comprises the processing aid of the present disclosure and a thermoplastic resin (A). The processing aid of the present disclosure may be added directly to a target material such as a thermoplastic resin, but adding it in the form of a masterbatch provides a better effect in improving processability in that it provides metering stability and good dispersibility.

[0213] Examples of the thermoplastic resin (A) include polyolefin polymers (polyethylene (PE)-polypropylene (PP)-ethylene-propylene copolymers), polystyrene (PS), AS (acrylonitrile styrene) resins (AS), ABS (acrylonitrile butadiene styrene) resins (ABS), methacrylic resins (PMMA), polymethylpentene (PMP), butadiene resins (BDR), polybutene-1 (PB-1), polyvinyl alcohol (PVA), polyacrylonitrile (PAN), polymethacrylic styrene (MS), ethylene-vinyl acetate copolymers (EVA), ethylene-vinyl alcohol copolymers, polyvinyl chloride (PVC), and the like. These may be used alone or in combination of two or more. Polyolefin polymers (polyolefin resins) are preferred because they provide a better effect of improving processability.

[0214] Among the polyolefin polymers, for example, homopolymers (for example, homopolymers of C2-C10 α-olefins, preferably homopolymers of C2-C6 α-olefins) can be mentioned. Specific examples of homopolymers include homopolyethylene and polypropylene (hPP). 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 of 0.945 g / cm. 3 Less than 0.935 g / cm 3 Less than or equal to, for example, 0.900, 0.905, or 0.910 g / cm 3to 0.920, 0.925, 0.927, 0.930, 0.935, or 0.945 g / cm 3 Unless otherwise noted herein, all polymer density values ​​are determined in accordance with ASTM D1505. Samples are molded under ASTM D4703-10a, procedure C, and conditioned under ASTM D618-08 (23±2°C and 50±10% relative humidity) for 40 hours prior to testing.

[0215] In another example, ethylene monomer can be polymerized using known gas, slurry, and / or solution phase polymerizations (e.g., catalysts such as chromium-based catalysts, or single-site catalysts such as Ziegler-Natta and / or metallocene catalysts, all of which are well known in the polymerization art and will not be discussed further herein. When a more highly linear ethylene homopolymer is produced (e.g., using gas or slurry phase polymerization with any of the above catalysts), it is referred to as HDPE (high density polyethylene), and typically has a density of 0.945 to 0.970 g / cm. 3 In the range of 0.945 g / cm 3 It has a density of more than 10 ...

[0216] 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, such as C4-C12 α-olefin comonomers (1-butene, 1-hexene, 1-octene, or mixtures of two or more thereof are preferred in various embodiments). The ethylene copolymer (e.g., a copolymer of ethylene and one or more C3-C20 α-olefins) can comprise ethylene-derived units in an amount of at least 90, 94, 95, or 96 wt% (e.g., from a low of 80, 85, 90, 80, 85, 93, 93, 95, 96, or 97 wt% to a high of 94, 95, 95.5, 91, 92, 97, 94, 97.5, or 98 wt%), including a range from any of the above lower values ​​to any of the above higher values, based on the total amount of ethylene-derived units and comonomer-derived units. For example, the ethylene copolymer can comprise ethylene-derived units in an amount of at least 90, 94, 95, or 96 wt% (e.g., from a low of 80, 85, 90, 80, 85, 93, 93, 95, 96, or 97 wt% to a high of 94, 95, 95.5, 91, 92, 97, 94, 97.5, or 98 wt%). In the ethylene copolymer, the copolymer may contain 94 or 95% to 97 or 98% by weight of ethylene-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 to C20 α-olefins such as units derived from butene, hexene and / or octene) may be present in the ethylene copolymer from a low value of 2, 2.5, 3, 3.5, 4, 4.5, 5, or 6% by weight to a high value of 3, 4, 5, 6, 7, 8, 9, 10, 15, or 20% by weight, ranging from the low value to the high value contemplated above (provided that the high value is greater than the low value).

[0217] For ethylene-based, propylene-based, or other α-olefin-based copolymers, some 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 may be used if necessary. Examples of suitable comonomers include linear C3-C20 α-olefins (such as butene, hexene, octene, etc., as already mentioned), and α-olefins with one or more C1-C3 alkyl branched or aryl groups. For example, it includes propylene; 3-methyl-1-butene; 3,3-dimethyl-1-butene; 1-pentene; 1-pentene with one or more methyl, ethyl or propyl substituents; 1-hexene with one or more methyl, ethyl or propyl substituents; 1-heptene with one or more methyl, ethyl or propyl substituents; 1-octene with one or more methyl, ethyl or propyl substituents; 1-nonene with one or more methyl, ethyl or propyl substituents; ethyl, methyl or dimethyl substituted 1-decene; 1-dodecene; and styrene. The above list of comonomers is merely illustrative and is not intended to be limiting. In some embodiments, the comonomer includes propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene and styrene.

[0218] In certain embodiments, the polymer may comprise or be (in accordance with those described above) an ethylene copolymer. The ethylene copolymer may be produced by gas, slurry or solution phase polymerization, with some particularly preferred ethylene copolymers being produced by gas or slurry phase polymerization. A particular example is linear low density polyethylene (LLDPE), a copolymer of ethylene and one or more α-olefins, 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 LLDPEs have viscosity profiles of 0.900, 0.905, 0.907, 0.910 g / cm 3from low concentrations of 0.920, 0.925, 0.930, 0.935, 0.940, or 0.945 g / cm 3 The density of the LLDPE may be in the range of 0.902 to 0.945, 0.906 to 0.932, or 0.908 to 0.926. LLDPE can be distinguished from the LDPEs described above in several ways, many of which are well known in the art, including the degree of branching (often little, if any) in the polymer produced, noting that LLDPE has substantially less long chain branching. In certain embodiments, the polymer of the polymer composition is or comprises a metallocene-catalyzed LLDPE (mLLDPE). In yet other embodiments, the polymer of the polymer composition is or comprises a Ziegler-Natta-catalyzed LLDPE (or ZN-LLDPE).

[0219] The density of the polymer may also be, in some embodiments, from 0.905 to 0.945 g / cm 3 for example, 0.905, 0.907, 0.908, 0.910, 0.911, 0.912, 0.913, 0.914, or 0.915 g / cm 3 from the lower 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 to any higher value, the range being from the lower to higher values ​​contemplated herein (e.g., 0.910 to 0.925 or 0.935 g / cm 3 , e.g. 0.912 to 0.925 or 0.915 to 0.918 g / cm 3 In yet another embodiment, the polymer has a viscosity of 0.945 g / cm 3 from 0.970 g / cm 3 It may also be of higher density (eg, HDPE) having a density in the range

[0220] Furthermore, the rheological properties of the polymer can affect the processing aid composition to form the molding. In general, the PPA composition is preferably used in polymers having a melt index (MI or I2 measured at 190° C. and 2.16 kg load according to ASTM D1238) of 1.5 g / 2.0 min or less, preferably 2.5 g / 3.0 min or less, such as within the range of 0.1, 0.2, or 0.5 g / 10 min to 1.0, 1.2, 5.0, 10, 2.5, 10, 4.0, or 5.0 g / 10 min. The melt index ratio (MIR), (MIR defined herein as the ratio of high load melt index (HLMI) (measured per ASTM D1238 at 190° C. under a load of 21.6 kg) to melt index, or HLMI / MI), in some embodiment polymers can have an MIR generally within 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. Optionally, the MI in such polymers can be less than 1.5 g / 10 min, such as 1.0 g / 10 min or less (e.g., 0.1, 0.2, or 0.5 g / 10 min to 1.0; or less than any of 1.1, 1.2, 1.3, 1.4, or 1.5 g / 10 min).

[0221] The LLDPE is preferably at least one selected from the group consisting of Ziegler-Natta catalyst type LLDPE and metallocene catalyst type LLDPE, and particularly preferably metallocene catalyst type LLDPE.

[0222] The thermoplastic resin (A) may be crystalline or non-crystalline. When the thermoplastic resin (A) is crystalline, it preferably has a melting point of 80 to 300° C., more preferably a melting point of 100 to 200° C. The non-crystalline thermoplastic resin (A) preferably has a processing temperature approximately equal to that of the crystalline thermoplastic resin (A) having a melting point range.

[0223] In the masterbatch of the present disclosure, the mass ratio of the thermoplastic resin (A) and the processing aid (thermoplastic resin (A):processing aid) is preferably 99:1 to 1:99. The mass ratio is more preferably 97:3 to 50:50, further preferably 95:5 to 60:40, and particularly preferably 92:8 to 70:30. The mass ratio may be 99:1 to 5:95, 90:10 to 7:93, 75:35 to 8:92, or 30:70 to 10:90.

[0224] In the masterbatch of the present disclosure, the total content of the thermoplastic resin (A) and the processing aid is preferably 80 mass% or more, more preferably 90 mass% or more, even more preferably 95 mass% or more, and particularly preferably 100 mass%.

[0225] The melt flow rate (MFR) of the masterbatch of the present disclosure is preferably 0.01 g / 10 min or more, more preferably 0.1 g / 10 min or more, even more preferably 1.0 g / 10 min or more, and is preferably 100 g / 10 min or less, more preferably 50 g / 10 min or less, even more preferably 20 g / 10 min or less. If it is within the above range, the effect of improving processability will be better. In this specification, the MFR is measured in accordance with ASTM D 1238 under conditions of 190° C. and a load of 2.16 kgf.

[0226] The masterbatch of the present disclosure may contain components other than the thermoplastic resin (A) and the processing aid.

[0227] The masterbatch of the present disclosure may be obtained, for example, by carrying out a mixing step of previously preparing the processing aid of the present disclosure and adding it to a mixer or the like together with the thermoplastic resin (A) and a discharging step of discharging the mixture from the mixer, etc., or by carrying out a mixing step of adding the thermoplastic resin (A) and the biodegradable polymer to a mixer or the like and mixing them, and a discharging step of discharging the mixture from the mixer, etc. The present disclosure also relates to a method for producing the above-mentioned masterbatch, which includes the mixing step and the discharging step.

[0228] In the method for producing a masterbatch according to the present disclosure, after the discharging step, a molding step of molding the discharged material using a molding machine or the like may be carried out.

[0229] The mixing step, the discharging step, and the 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. The shape of the masterbatch of the present disclosure is not particularly limited and may be powder, granules, pellets, etc., but pellets are preferred because they are easy to handle and mold.

[0230] The masterbatches of the present disclosure are particularly useful as masterbatches for improving the processability of thermoplastic resins, particularly polyolefin resins.

[0231] <Thermoplastic resin composition> The thermoplastic resin composition of the present disclosure contains the processing aid of the present disclosure and / or the masterbatch of the present disclosure and a thermoplastic resin (B), which provides good processability (particularly extrusion processability).

[0232] As the thermoplastic resin (B), the same ones as the thermoplastic resin (A) can be used, and the preferred forms are also the same.

[0233] The thermoplastic resin composition of the present disclosure may contain at least one of the processing aid of the present disclosure and the masterbatch of the present disclosure, but it is preferable that the thermoplastic resin composition of the present disclosure contains the masterbatch of the present disclosure in that better processability can be obtained.

[0234] When the thermoplastic resin composition of the present disclosure contains the masterbatch of the present disclosure, the thermoplastic resin (A) and the thermoplastic resin (B) may be the same type or different types.

[0235] In the thermoplastic resin composition of the present disclosure, the content of the processing aid is preferably 0.001% by mass or more, more preferably 0.01% by mass or more, even more preferably 0.06% by mass or more, even more preferably 0.10% by mass or more, particularly preferably 0.15% by mass or more, and also preferably 5.0% by mass or less, more preferably 3.0% by mass or less, even more preferably 2.0% by mass or less, particularly preferably 1.5% by mass or less. The content may be 0.001% by mass or more, 0.01% by mass or more, 0.1% by mass or more, 0.3% by mass or more, 0.5% by mass or more, 5% by mass or less, 2% by mass or less, 1.5% by mass or less, or 1.0% by mass or less.

[0236] The thermoplastic resin composition of the present disclosure may contain components other than the processing aid, the masterbatch, and the thermoplastic resin (B). Examples of components that can be used other than the processing aid, the master batch, and the thermoplastic resin (B) include anti-adhesion agents; ultraviolet absorbers; flame retardants; reinforcing materials such as glass fiber and glass powder; stabilizers such as minerals and flakes; lubricants such as silicone oil and molybdenum disulfide; pigments such as titanium dioxide and red iron oxide; conductive agents such as carbon black; impact resistance improvers such as rubber; hindered phenol-based and phosphorus-based antioxidants; nucleating agents such as metal salts and acetals of sorbitol, anti-blocking agents, and the above-mentioned lubricant (A).

[0237] The thermoplastic resin composition of the present disclosure may be obtained, for example, by previously preparing the master batch of the present disclosure, feeding the master batch into a mixer or the like together with the thermoplastic resin (B) and carrying out a mixing step of mixing and discharging the mixture from the mixer or the like, or by feeding the thermoplastic resin (B), the biodegradable polymer, and, if necessary, the thermoplastic resin (A) into a mixer or the like, carrying out a mixing step of mixing and discharging the mixture from the mixer or the like. The present disclosure is also a method for producing the above-mentioned thermoplastic resin composition, including the mixing step and the discharging step.

[0238] In the method for producing a 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.

[0239] The mixing step, the discharging step, and the molding step in the method for producing a thermoplastic resin composition of the present disclosure are the same as those described in the method for producing a processing aid of the present disclosure.

[0240] <Molded body> The molded article of the present disclosure uses the thermoplastic resin composition of the present disclosure, and may be, for example, obtained by carrying out a molding step of molding the thermoplastic resin composition of the present disclosure. The present disclosure also relates to a method for producing the molded article of the present disclosure, the method including a molding step. The thermoplastic resin composition of the present disclosure is suitable for molding into a tube-shaped, film-shaped, or sheet-shaped article, but can also be applied to molded articles of other shapes.

[0241] The molding step is the same as that described in the method for producing the processing aid of the present disclosure.

[0242] In the molding step, the molding temperature (extrusion temperature) is generally set to a temperature equal to or higher than the melting point of the thermoplastic resin (B) and lower than the decomposition temperature of the biodegradable polymer. In order to ensure that the effect of the processing aid is significantly exhibited, the temperature is preferably in the range of 160°C to 270°C. In the case of extrusion molding, the molding temperature may be referred to as the extrusion temperature.

[0243] Applications of the molded article of the present disclosure are not particularly limited, but examples include bags, covering materials, tableware such as beverage containers, electric wires, cables, pipes, fibers, bottles, gasoline tanks, and various other industrial molded articles.

[0244] <Film> The film of the present disclosure uses the thermoplastic resin composition of the present disclosure, and may be obtained, for example, by carrying out a molding step of molding the thermoplastic resin composition of the present disclosure. The present disclosure also relates to a method for producing the molded article of the present disclosure, the method including a molding step. The thermoplastic resin composition of the present disclosure is suitable for molding into a tube-shaped, film-shaped, or sheet-shaped article, but can also be applied to molded articles of other shapes.

[0245] The molding step is the same as that described in the method for producing the processing aid of the present disclosure.

[0246] In the molding step, the molding temperature (extrusion temperature) is generally set to a temperature equal to or higher than the melting point of the thermoplastic resin (B) and lower than the decomposition temperature of the biodegradable polymer. In order to ensure that the effect of the processing aid is significantly exhibited, the temperature is preferably in the range of 160°C to 270°C. In the case of extrusion molding, the molding temperature may be referred to as the extrusion temperature.

[0247] Applications of the films of the present disclosure are not particularly limited, but include, for example, bags, covering materials, tableware such as beverage containers, electric wires, cables, pipes, fibers, bottles, gasoline tanks, and various other industrial molded products.

[0248] 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

[0249] Next, the present disclosure will be described with reference to examples, but the present disclosure is not limited to only these examples.

[0250] In the examples and comparative examples, the following materials were used. (Additives (biodegradable polymers)) PBS-1: Polybutylene succinate (MFR: 22g / 10min, melting point: 114℃) PBS-2: Polybutylene succinate (MFR: 4g / 10min, melting point: 85℃) PBS-3: Polybutylene succinate (MFR: 250g / 10min, melting point: 114℃) PLA-1: Polylactic acid (MFR: 3g / 10min, melting point: 153℃) PLA-2: Polylactic acid (MFR: 30g / 10min, melting point: 172℃) PLA-3: Polylactic acid (MFR: 110g / 10min, melting point: 174℃) PBAT: Polybutylene adipate terephthalate (MFR: 4g / 10min, melting point: 115℃) (Additives (Synergists)) PCL: Polycaprolactone (Mw: 80,000, melting point: 55°C) PEG-1: Polyethylene glycol (Mn: 8,000, melting point: 63°C) PEG-2: Polyethylene glycol (Mn: 35,000, melting point: 63°C) PEO-1: Polyethylene oxide (Mv: 150,000-400,000, melting point: 64°C) PEO-2: Polyethylene oxide (Mv: 400,000-600,000, melting point: 65°C) PEO-3: Polyethylene oxide (Mv: 600,000-1,100,000, melting point: 66°C) MB50-002: Silicone (Ultra-high molecular weight silicone-containing masterbatch, manufactured by Dupont) GENIOPLAST PELLET S: Silicone (ultra-high molecular weight silicone, manufactured by Wacker Asahi Kasei) Pebax MV1072: Polyamide-polyether block copolymer (Arkema) (Additive (Ethylene-vinyl alcohol copolymer)) EVOH-1: Ethylene-vinyl alcohol copolymer (ethylene content: 38 mol%, MFR: 1.5 g / 10 min) EVOH-2: Ethylene-vinyl alcohol copolymer (ethylene content: 32 mol%, MFR: 1.6 g / 10 min) EVOH-3: Ethylene-vinyl alcohol copolymer (ethylene content: 44 mol%, MFR: 1.6 g / 10 min) EVOH-4: Ethylene-vinyl alcohol copolymer (ethylene content: 38 mol%, MFR: 50 g / 10 min) (Additives (lubricants (A))) Polysorbate 60: Polysorbate 60 Zn-St: Zinc stearate (zinc stearate) Mg-C18(OH): Magnesium 12-hydroxystearate (Additives (antideterioration agents)) Phenols: Pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] Phosphate: Tris(2,4-di-tert-butylphenyl) phosphite (Matrix resin, carrier resin) LLDPE-1: Metallocene-catalyzed linear low-density polyethylene (MFR: 0.7 g / 10 min, melting point: 123°C, d=0.926, MIR=28.1) LLDPE-2: Metallocene-catalyzed linear low-density polyethylene (MFR: 2.0 g / 10 min, melting point: 121°C, d=0.925, MIR=23.6) LLDPE-3: Ziegler-Natta catalyst type linear low density polyethylene (MFR: 0.8g / 10min, melting point: 123℃, d=0.925, MIR=27.0) LLDPE-4: Ziegler-Natta catalyst type linear low density polyethylene (MFR: 2.0g / 10min, melting point: 121℃, d=0.918, MIR=23.2) LDPE: Low density polyethylene (MFR: 2.0g / 10min, melting point: 111℃, d=0.924)

[0251] MFR: The MFR (g / 10 min) of the above additives, matrix resin, and carrier resin was measured in accordance with ASTM D 1238 under conditions of 190° C. and a load of 2.16 kgf.

[0252] MIR: The MIR of the matrix resin and carrier resin was determined by HLMI / MI. HLMI: Compliant with ASTM D 1238, MFR (g / 10min) at 190℃ and 21.6kgf load MI: Compliant with ASTM D 1238, MFR (g / 10min) at 190℃ and a load of 2.16kgf

[0253] Melting Point: Using a DSC device (manufactured by Seiko Corporation), the temperature corresponding to the maximum value in the heat of fusion curve when the temperature was raised at a rate of 10° C. / min was taken as the melting point.

[0254] Examples A1 to A15, Comparative Examples A1 to A10 Thermoplastic resin compositions were obtained by dry blending each material with a matrix resin (LLDPE-1) in the ratios shown in Table 1. The processability of the obtained thermoplastic resin compositions was evaluated by the following extrusion evaluation. The results are shown in Table 1. In addition, in Comparative Examples A3 to A10, extrusion was impossible due to slippage.

[0255] Examples B1 to B8, Comparative Examples B1 to B6 First, additives were dry-blended in the ratios shown in Table 2 to obtain a processing aid. Next, the obtained processing aid was dry-blended with a matrix resin (LLDPE-1) in the ratios shown in Table 2 to obtain a thermoplastic resin composition. The processability of the obtained thermoplastic resin composition was evaluated by the following extrusion evaluation. The results are shown in Table 2. In addition, in Comparative Examples B3 to B6, extrusion was impossible due to slippage.

[0256] Examples C1 to C15, Comparative Examples C1 to C10, Examples D1 to D9, Comparative Examples D1 to D11 First, the carrier resin and additives were melt-kneaded in the ratios shown in Tables 3 and 4 using a twin-screw extruder (TEXαIII manufactured by Japan Steel Works, Ltd.) under 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 master batch (MB). Next, the obtained master batch was dry-blended with a matrix resin (LLDPE-1) in the ratios shown in Tables 3 and 4 to obtain a thermoplastic resin composition. The processability of the obtained thermoplastic resin composition was evaluated by the following extrusion evaluation. The results are shown in Tables 3 and 4.

[0257] Examples E1 to E13, Comparative Example E1 First, additives were dry-blended in the ratios shown in Table 5 to obtain a processing aid. Next, the obtained processing aid was dry-blended with a matrix resin (LLDPE-1) in the ratios shown in Table 5 to obtain a thermoplastic resin composition. The processability of the obtained thermoplastic resin composition was evaluated by the following extrusion evaluation. The results are shown in Table 5.

[0258] Examples F1 to F16, Comparative Example F1 First, the carrier resin and additives were melt-kneaded in the ratios shown in Table 6 using a twin-screw extruder (TEXαIII manufactured by Japan Steel Works, Ltd.) under 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 master batch (MB). Next, the obtained master batch was dry-blended with a matrix resin (LLDPE-1) in the ratios shown in Table 6 to obtain a thermoplastic resin composition. The processability of the obtained thermoplastic resin composition was evaluated by the following extrusion evaluation. The results are shown in Table 6.

[0259] In addition, the following contents are the same in Tables 1 to 4. Examples A3 and B7 Examples A10 and B8 Examples C3 and D8 Examples C10 and D9 Comparative examples A1, B1, C1, E1, F1 Comparative examples A2, B2

[0260] <Extrusion evaluation> Each material was extruded for 60 minutes using a single-screw extruder (HAAKE, Rheomex OS, L / D: 33, screw diameter: 20 mm, die diameter: 2 mm) under conditions of a cylinder temperature of 170 to 200°C, a die temperature of 200°C, and a shear rate of 450 / sec., and evaluated for the following items. Before each test run, linear low-density polyethylene containing 15% silica was added to the hopper, the screw speed was increased to 150 rpm, and purging was performed for about 15 minutes. Next, the same LLDPE-1 used in the test was added and purging was performed for about 15 minutes, after which the screw speed was returned to 30 rpm and extrusion was performed until the temperature stabilized. After confirming that the initial pressure had returned, the next experiment was performed. If the initial pressure had not returned, the above purging process was repeated until the initial pressure returned, and then the next experiment was performed. (Melt fracture (MF) state) Extrusion was performed until the pressure stabilized with only the matrix resin and melt fracture occurring all over the surface, and the point at which the screw was visible was set as zero, and extrusion was continued for 60 minutes. In cases where a processing aid or masterbatch was used, these were added to the hopper at zero point. The appearance of the strands at the beginning of extrusion and at the end of extrusion was then visually and tactilely confirmed, and the change in MF observed at the beginning of extrusion was evaluated according to the following criteria. The smaller the value, the better. 1: MF completely disappears 2: MF decreases but does not disappear completely 3: MF is the same as when only the matrix resin is used, or there is almost no decrease (Pressure stability) After the start of extrusion, the extrusion pressure was measured for 50 to 60 minutes, and the standard deviation was calculated. The closer the value is to 0, the better the result. (Die Build Up (DBU)) The condition of the die after extrusion was visually inspected and evaluated for the presence or absence of DBU (eye discharge). In Tables 1 to 4, the evaluation was made on a three-point scale based on the following criteria. The smaller the value, the better the result. 1: No DBU occurred 2: A small amount of DBU occurs 3: Large amount of DBU occurs In Tables 5 and 6, the evaluation was made on a five-level scale from 1 to 5. The smaller the value, the less DBU was generated and the better the result, with 1 indicating that no DBU was generated. In addition, Tables 1 to 4 show both a three-point scale and a five-point scale. (Melt fracture (MF) disappearance time) The time from the zero point described above for the MF condition to the disappearance of the MF was measured. The shorter the time, the better. Those that did not disappear after 60 minutes of extrusion were marked with "-".

[0261] [Table 1]

[0262] [Table 2]

[0263] [Table 3]

[0264] [Table 4]

[0265] [Table 5]

[0266] [Table 6] Examples 1 to 83, Comparative Examples 1 to 3 First, the carrier resin and additives were melt-kneaded in the ratios shown in Tables 7 to 9 using a twin-screw extruder (TEX25αIII manufactured by Japan Steel Works, Ltd.) under conditions of a cylinder temperature of 180 to 200°C, a die temperature of 200°C, and a screw rotation speed of 400 rpm so that the concentration of the additives was 25% by mass, to obtain a master batch (MB). Next, the obtained master batch was dry-blended with a matrix resin in the ratios shown in Tables 7 to 9, and the processability was evaluated by the following extrusion evaluation. The results are shown in Tables 7 to 9. Note that since none of the additive materials used contained fluorine, the fluorine content in the processing aid was 0% by mass.

[0267] <Extrusion evaluation> For Examples 1 to 72 and Comparative Examples 1 to 3, each material was extruded for 60 minutes using a single-screw extruder (HAAKE, Rheomex OS, L / D: 33, screw diameter: 20 mm, die diameter: 2 mm) under conditions of a cylinder temperature of 170 to 200°C, a die temperature of 200°C, and a shear rate of 450 / sec, and evaluated for the following items. Before each test run, linear low-density polyethylene containing 15% by mass of silica was added to the hopper, the screw 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 added and purging was performed for about 15 minutes, after which the screw speed was returned to 30 rpm and extrusion was performed until the temperature stabilized. After confirming that the initial pressure had returned, the next experiment was performed. If the initial pressure had not returned, the above purging operation was repeated until the initial pressure returned, and then the next experiment was performed. (Melt fracture (MF) state) Extrusion was performed until the pressure stabilized with only the matrix resin and melt fracture occurring all over the surface, and the point at which the screw was visible was set as zero, and extrusion was continued for 60 minutes. In cases where a processing aid or masterbatch was used, these were added to the hopper at zero point. The appearance of the strands at the beginning of extrusion and at the end of extrusion was then visually and tactilely confirmed, and the change in MF observed at the beginning of extrusion was evaluated according to the following criteria. The smaller the value, the better. Disappearance: MF completely disappears Not disappeared: MF is the same as when only the matrix resin is used, or MF decreases but does not disappear completely. (Die Build Up (DBU)) For samples in which MF had completely disappeared, extrusion evaluation was performed using long-run molding (3 hours), and the state of the die after extrusion was visually confirmed and the presence or absence of DBU (eye discharge) was evaluated. The evaluation was made on a 5-point scale from 1 to 5. The smaller the value, the less DBU was generated and the better the result, with 1 indicating that no DBU was generated. (Storage stability test) For Examples 29, 36, 41, 46, and 47, strand samples were taken after long-run molding (3 hours) and left to stand for 24 hours at 80°C. After 24 hours, a sensory evaluation (touch) was performed on the slipperiness of the strand surface, and the slipperiness before and after the test was evaluated according to the following criteria. The results are shown in Table 8. Yes: The slipperiness is higher after the test than before the test None: No change before and after the test

[0268] <Film molding> For Examples 73 to 83, each material was extruded for 70 minutes using a single-layer inflation molding machine (inflation die diameter 25 mm, die gap 0.8 mm) under conditions of cylinder temperature 170°C, die temperature 200°C, and shear rate 90 / sec, and evaluated for the following items. Before each test run, linear low-density polyethylene containing 15% by mass of silica was put into the hopper and purged for about 60 minutes. Next, the same matrix resin as that used in the test was put in and purged for about 60 minutes, and the next experiment was performed after confirming that the initial pressure had returned. If the initial pressure had not returned, the above purging operation was repeated until the initial pressure returned, and then the next experiment was performed.

[0269] (Melt fracture (MF) state) Extrusion was continued until the pressure stabilized with only the matrix resin and melt fracture occurring all over the surface, and the point at which the screw was visible was recorded as time zero, and extrusion was continued for 70 minutes. In cases where a processing aid or masterbatch was used, these were added to the hopper at time zero. The appearance of the film at the beginning of extrusion and after the start of extrusion was confirmed by visual inspection and palpation, and the time at which it disappeared was recorded. The shorter the time, the better. The results are shown in Table 9.

[0270] (Pressure stability) After 5 minutes had elapsed since the disappearance of the MF, 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 the result. The results are shown in Table 9.

[0271] (film thickness) After the start of film extrusion, a 3-minute film was sampled at 50, 60, and 70 minutes. For each sampled film, one measurement point was set in the film TD direction, and the film thickness was measured at 25 points in the MD direction at 25°C (total of 75 points), and the average, maximum, and minimum values ​​were calculated. The thickness unevenness was then calculated using the following formula. The results are shown in Table 9. Thickness unevenness (%) = (Maximum thickness (maximum value) - Minimum thickness (minimum value)) / Average thickness (average value) x 100

[0272] <Masterbatch MFR> For Examples 84 to 91, the carrier resin and additives were melt-kneaded in the ratios shown in Table 10 using a twin-screw extruder (TEX25αIII manufactured by Japan Steel Works, Ltd.) under conditions of cylinder temperature 180 to 200°C, die temperature 200°C, and screw rotation speed 400 rpm so that the concentration of additives was 25 mass%, to obtain a master batch (MB). The MFR (g / 10 min) of the obtained master batch was measured (based on ASTM D 1238, conditions of 190°C and load 2.16 kgf). The results are shown in Table 10.

[0273] [Table 7]

[0274] [Table 8]

[0275] [Table 9]

[0276] [Table 10]

Claims

1. A processing aid comprising a biodegradable polymer having a melting point of 65°C or higher.

2. 2. The processing aid according to claim 1, wherein the biodegradable polymer has a melting point of 190° C. or lower.

3. 3. The processing aid according to claim 1, wherein the biodegradable polymer is an aliphatic polyester.

4. 4. The processing aid according to claim 3, wherein the aliphatic polyester is at least one selected from the group consisting of polylactic acid and polybutylene succinate.

5. 3. The processing aid according to claim 1, wherein the biodegradable polymer has a melt flow rate of 0.01 to 500 g / 10 min at 190° C. under a load of 2.16 kgf.

6. 3. The processing aid according to claim 1, further comprising a synergist which is at least one member selected from the group consisting of polyols having a melting point of 80° C. or less, polycaprolactones, silicones, and polyamide-polyether block copolymers.

7. The processing aid according to claim 6, wherein the polyol is polyethylene glycol and / or polyethylene oxide.

8. The processing aid according to claim 7, wherein the number average molecular weight of the polyethylene glycol is 1,000 to 50,000, the viscosity average molecular weight of the polyethylene oxide is 100,000 to 10,000,000, and the weight average molecular weight of the polycaprolactone is 2,000 to 100,000.

9. The processing aid according to claim 6, wherein the mass ratio of the biodegradable polymer to the synergist (biodegradable polymer:synergist) is 99.9:0.1 to 10:

90.

10. 3. The processing aid according to claim 1 or 2, which comprises an ethylene-vinyl alcohol copolymer.

11. The processing aid according to claim 10, wherein the ethylene-vinyl alcohol copolymer has a melt flow rate of 40 g / 10 min or less at 190° C. and a load of 2.16 kgf.

12. The processing aid according to claim 10, wherein the ethylene-vinyl alcohol copolymer has an ethylene content of 10 to 50 mol %.

13. The processing aid according to claim 10, wherein the mass ratio of the biodegradable polymer to the ethylene-vinyl alcohol copolymer (biodegradable polymer:ethylene-vinyl alcohol copolymer) is 95:5 to 10:

90.

14. The processing aid according to claim 10, wherein the mass ratio of the biodegradable polymer to the ethylene-vinyl alcohol copolymer (biodegradable polymer:ethylene-vinyl alcohol copolymer) is 92:8 to 70:

30.

15. The processing aid according to claim 10, wherein a mass ratio of the biodegradable polymer, the ethylene-vinyl alcohol copolymer, and the synergist (biodegradable polymer:ethylene-vinyl alcohol copolymer:synergist) is 1-98:1-98:1-98.

16. The processing aid according to claim 10, wherein the mass ratio of the biodegradable polymer, the ethylene-vinyl alcohol copolymer and the synergist (biodegradable polymer:ethylene-vinyl alcohol copolymer:synergist) is 25-90:5-70:5-70.

17. 3. The processing aid according to claim 1, further comprising a lubricant (A) which is at least one selected from the group consisting of waxes, alcohols and surfactants.

18. The processing aid according to claim 17, wherein the mass ratio of the biodegradable polymer to the lubricant (A) (biodegradable polymer:lubricant (A)) is 99:1 to 1:

99.

19. The processing aid according to claim 17, wherein the mass ratio of the biodegradable polymer to the lubricant (A) (biodegradable polymer:lubricant (A)) is 90:10 to 40:

60.

20. The processing aid according to claim 17, wherein the mass ratio of the biodegradable polymer, the ethylene-vinyl alcohol copolymer, and the lubricant (A) (biodegradable polymer:ethylene-vinyl alcohol copolymer:lubricant (A)) is 1-98:1-98:1-98.

21. The processing aid according to claim 17, wherein the mass ratio of the biodegradable polymer, the ethylene-vinyl alcohol copolymer, and the lubricant (A) (biodegradable polymer:ethylene-vinyl alcohol copolymer:lubricant (A)) is 25-93:5-70:2-70.

22. 3. The processing aid according to claim 1 or 2, which is substantially free of fluorine.

23. A masterbatch comprising the processing aid according to claim 1 and a thermoplastic resin (A).

24. The masterbatch according to claim 23, wherein the thermoplastic resin (A) is a polyolefin resin.

25. 25. The masterbatch according to claim 24, wherein the polyolefin resin is polyethylene.

26. The masterbatch according to claim 23, wherein the mass ratio of the thermoplastic resin (A) to the processing aid (thermoplastic resin (A): processing aid) is 99:1 to 5:

95.

27. The masterbatch according to claim 23, which has a melt flow rate of 0.01 to 100 g / 10 min at 190° C. and a load of 2.16 kgf.

28. A thermoplastic resin composition comprising the processing aid according to claim 1 or 2 and / or the masterbatch according to claim 23 or 24, and a thermoplastic resin (B).

29. The thermoplastic resin composition according to claim 28, wherein the thermoplastic resin (B) is a polyolefin resin.

30. 30. The thermoplastic resin composition according to claim 29, wherein the polyolefin resin is polyethylene.

31. The thermoplastic resin composition according to claim 28, wherein the content of the processing aid is 0.001 to 5 mass%.

32. A film using the thermoplastic resin composition according to claim 28.

33. The method for producing the processing aid according to claim 1 or 2, comprising a mixing step and a discharging step.

34. The method for producing the masterbatch according to claim 23 or 24, comprising a mixing step and a discharging step.

35. 29. The method for producing the thermoplastic resin composition according to claim 28, comprising the steps of mixing and discharging.

36. 33. A method for producing the film of claim 32, comprising a molding step.

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