Processing aid, master batch, thermoplastic resin composition, and film

Abstract

The present disclosure provides a processing aid and a master batch capable of improving the processability of a thermoplastic resin, and a thermoplastic resin composition and a film using the same. The present disclosure is a processing aid comprising a biodegradable polymer having a melting point of 65 DEG C or higher.

Description

Technical Field

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

[0002] In the processing of melt-processable thermoplastic resins, high extrusion speed is required to improve productivity and reduce costs. However, melt-processable thermoplastic resin compositions inevitably have a critical shear rate. Exceeding this rate causes a surface roughening known as melt fracture, preventing the production of good molded products.

[0003] As a method for improving the processability of thermoplastic resins, processing aids containing high molecular weight polyethylene glycol are proposed, for example, in Patent Documents 1 and 2. However, the effects thereof are not sufficient.

[0004] Prior art literature

[0005] Patent Literature

[0006] Patent Document 1: Japanese Patent Application No. 2017-538833

[0007] Patent Document 2: U.S. Patent Application Publication No. 2005 / 0070644 Summary of the Invention

[0008] Technical problem to be solved by the invention

[0009] An object of the present disclosure is to provide a processing aid and a masterbatch capable of improving the processability of a thermoplastic resin, and a thermoplastic resin composition and a film using the same.

[0010] Means of solving technical problems

[0011] The present disclosure (1) is a processing aid comprising a biodegradable polymer having a melting point of 65° C. or higher.

[0012] 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.

[0013] The present disclosure (3) is the processing aid according to the present disclosure (1) or (2), wherein the biodegradable polymer is an aliphatic polyester.

[0014] The present disclosure (4) is the processing aid described in the present disclosure (3), wherein the aliphatic polyester is at least one selected from the group consisting of polylactic acid and polybutylene succinate.

[0015] 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. and a load of 2.16 kgf.

[0016] The present disclosure (6) is the processing aid described in any one of the present disclosures (1) to (5), wherein the processing aid contains a synergist, which is at least one selected from the group consisting of polyols having a melting point of 80° C. or less, polycaprolactone, silicone, and polyamide-polyether block copolymers.

[0017] The present disclosure (7) is the processing aid described in the present disclosure (6), wherein the polyol is polyethylene glycol and / or polyethylene oxide.

[0018] The present disclosure (8) is the processing aid described in 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.

[0019] The present disclosure (9) is the processing aid according to any one of the present disclosures (6) to (8), wherein the mass ratio of the biodegradable polymer to the synergist (biodegradable polymer:synergist) is 99.9:0.1 to 10:90.

[0020] The present disclosure (10) is the processing aid according to any one of the present disclosures (1) to (9), comprising an ethylene-vinyl alcohol copolymer.

[0021] The present disclosure (11) is the processing aid described in the present disclosure (10), wherein the melt flow rate of the ethylene-vinyl alcohol copolymer at 190° C. and a load of 2.16 kgf is 40 g / 10 min or less.

[0022] The present disclosure (12) is the processing aid described in the present disclosure (10) or (11), wherein the ethylene content of the ethylene-vinyl alcohol copolymer is 10 to 50 mol%.

[0023] 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.

[0024] 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.

[0025] The present disclosure (15) is the processing aid described in any one of the present disclosures (10) to (14), wherein the mass ratio of the above-mentioned biodegradable polymer, the above-mentioned ethylene-vinyl alcohol copolymer and the above-mentioned synergist (biodegradable polymer: ethylene-vinyl alcohol copolymer: synergist) is 1 to 98:1 to 98:1 to 98.

[0026] The present disclosure (16) is the processing aid described in any one of the present disclosures (10) to (15), wherein the mass ratio of the above-mentioned biodegradable polymer, the above-mentioned ethylene-vinyl alcohol copolymer and the above-mentioned synergist (biodegradable polymer: ethylene-vinyl alcohol copolymer: synergist) is 25-90:5-70:5-70.

[0027] The present disclosure (17) is the processing aid according to any one of the present disclosures (1) to (16), comprising a lubricant (A), wherein the lubricant (A) is at least one selected from the group consisting of waxes, alcohols, and surfactants.

[0028] The present disclosure (18) is the processing aid described in the present disclosure (17), wherein the mass ratio of the above-mentioned biodegradable polymer to the above-mentioned lubricant (A) (biodegradable polymer:lubricant (A)) is 99:1 to 1:99.

[0029] The present disclosure (19) is the processing aid described in the present disclosure (17) or (18), wherein the mass ratio of the above-mentioned biodegradable polymer to the above-mentioned lubricant (A) (biodegradable polymer:lubricant (A)) is 90:10 to 40:60.

[0030] The present disclosure (20) is the processing aid described in any one of the present disclosures (17) to (19), wherein the mass ratio of the above-mentioned biodegradable polymer, the above-mentioned ethylene-vinyl alcohol copolymer and the above-mentioned lubricant (A) (biodegradable polymer: ethylene-vinyl alcohol copolymer: lubricant (A)) is 1 to 98:1 to 98:1 to 98.

[0031] The present disclosure (21) is a processing aid according to any one of the present disclosures (17) to (20), 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.

[0032] The present disclosure (22) is the processing aid described in any one of the present disclosures (1) to (21), which does not substantially contain fluorine.

[0033] The present disclosure (23) is a masterbatch comprising the processing aid described in any one of the present disclosures (1) to (22) and a thermoplastic resin (A).

[0034] The present disclosure (24) is the masterbatch described in the present disclosure (23), wherein the thermoplastic resin (A) is a polyolefin resin.

[0035] The present disclosure (25) is the masterbatch described in the present disclosure (24), wherein the polyolefin resin is polyethylene.

[0036] The present disclosure (26) is the masterbatch according to any one of the present disclosures (23) to (25), wherein the mass ratio of the thermoplastic resin (A) to the processing aid (thermoplastic resin (A): processing aid) is 99:1 to 5:95.

[0037] 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. and a load of 2.16 kgf.

[0038] The present disclosure (28) is a thermoplastic resin composition comprising the processing aid described in any one of the present disclosures (1) to (22) and / or the masterbatch described in any one of the present disclosures (23) to (27), and a thermoplastic resin (B).

[0039] The present disclosure (29) is the thermoplastic resin composition described in the present disclosure (28), wherein the thermoplastic resin (B) is a polyolefin resin.

[0040] The present disclosure (30) is the thermoplastic resin composition described in the present disclosure (29), wherein the polyolefin resin is polyethylene.

[0041] 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% by mass.

[0042] The present disclosure (32) is a film using the thermoplastic resin composition described in any one of the present disclosures (28) to (31).

[0043] The present disclosure (33) is a method for producing the processing aid according to any one of the present disclosures (1) to (22), which includes a mixing step and a discharging step.

[0044] The present disclosure (34) is a method for producing a masterbatch according to any one of the present disclosures (23) to (27), which includes a mixing step and a discharging step.

[0045] The present disclosure (35) is a method for producing a thermoplastic resin composition according to any one of the present disclosures (28) to (31), which includes a mixing step and a discharging step.

[0046] The present disclosure (36) is a method for manufacturing the film described in the present disclosure (32), which includes a molding step.

[0047] Effects of the Invention

[0048] According to the present disclosure, the processability of thermoplastic resin can be improved. DETAILED DESCRIPTION

[0049] The present disclosure is described in detail below.

[0050] <Processing aids>

[0051] The processing aid disclosed herein comprises a biodegradable polymer having a melting point of 65° C. or higher.

[0052] In this specification, the term "biodegradable polymer" refers to a biodegradable polymer that is degraded into low molecular weight compounds in nature by the participation of microorganisms. Examples thereof 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). Furthermore, PHA includes poly(3-hydroxybutyrate) (PHB), poly(3-hydroxybutyrate / 3-hydroxyvalerate) (PHBV), poly(3-hydroxybutyrate / 3-hydroxyhexanoate) (PHBH), poly(3-hydroxybutyrate / 4-hydroxybutyrate), and the like.

[0053] The polylactic acid is a polymer with L-lactic acid and / or D-lactic acid as the main constituents, and may contain other copolymer components besides lactic acid. Other monomer units include ethylene glycol, propylene glycol, butanediol, heptanediol, hexanediol, octanediol, nonanediol, decanediol, 1,4-cyclohexanedimethanol, neopentyl glycol, glycerol, pentaerythritol, bisphenol A, polyethylene glycol, polypropylene glycol, polytetramethylene glycol and other glycol compounds, oxalic acid, adipic acid, sebacic acid, azelaic acid, dodecanedioic acid, malonic acid, glutaric acid, cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid Dicarboxylic acids such as formic acid, phthalic acid, naphthalene dicarboxylic acid, bis(p-carboxyphenyl)methane, anthracene dicarboxylic acid, 4,4'-diphenyl ether dicarboxylic acid, 5-(sodiosulfo)isophthalic 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.

[0054] The molecular weight and molecular weight distribution of the biodegradable polymer are not particularly limited as long as the biodegradable polymer can be substantially processed by extrusion molding.

[0055] The processing aid disclosed herein is based on the discovery that the use of biodegradable polymers having a melting point of 65°C or higher significantly improves the processability of thermoplastic resins. Preferred biodegradable polymers having a melting point of 65°C or higher are aliphatic polyesters such as PLA and PBS, with PLA and PBS being particularly preferred.

[0056] The melting point of the biodegradable polymer may be 65°C or higher, preferably 70°C or higher, more preferably 75°C or higher, and even more preferably 80°C or higher, and preferably 190°C or lower, more preferably 185°C or lower, and even more preferably 180°C or lower. Within this range, the effect of improving processability is further enhanced.

[0057] 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 calorimeter (DSC) apparatus.

[0058] 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. Within this range, the effect of improving processability is further enhanced.

[0059] In this specification, MFR is measured in accordance with ASTM D 1238 under the conditions of 190° C. and a load of 2.16 kgf.

[0060] In the processing aid disclosed herein, the content of the biodegradable polymer is preferably 60% by mass or greater, more preferably 70% by mass or greater, and even more preferably 80% by mass or greater. The upper limit is not particularly limited and may be 100% by mass. When used in combination with a synergist described below, the content is preferably 99% by mass or less, and more preferably 95% by mass or less.

[0061] The biodegradable polymer preferably includes a structural unit represented by the following formula 1.

[0062] -X-(CR 1 R 2 ) n -Y-(CR 3 R 4 ) m -Z- (Formula 1)

[0063] (In Formula 1, X is a single bond or a divalent group with or without a functional group,

[0064] Y and Z are each independently a single bond, a group consisting of at least one member selected from the group consisting of -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' in each occurrence is independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms),

[0065] R 1 、R 2 、R 3 and R 4 are each independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms,

[0066] n and m are each independently an integer of 0 to 10,

[0067] At least one of X, Y, and Z is -C(=O)-, -C(=O)O-, -OC(=O)O-, or -C(OR')R'-.

[0068] In the above formula 1, X is preferably selected from 1 and X 2 A divalent group consisting of at least one of the group consisting of

[0069] X1 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 a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms in each occurrence),

[0070] X 2 It is an aromatic hydrocarbon group having 1 to 12 carbon atoms which may have a substituent.

[0071] 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' in each occurrence is independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms).

[0072] In the above formula 1, R' is 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.

[0073] In the above formula 1, it is preferred that Y and Z are each independently a single bond, a group consisting of at least one selected from the group consisting of -O-, -C(=O)-, -C(=O)O-, -C(=NR')-, -C(=NR')O-, -S-, -S(=O)2-, -S(=O)2O-, -NR'- and -C(OR')R'- (wherein R' is independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms in each occurrence).

[0074] In the above formula 1, it is preferred that Y and Z each independently represent a single bond or a group consisting of at least one selected from the group consisting of -O-, -C(=O)-, and -C(=O)O-.

[0075] In the above formula 1, R 1 、R 2 、R 3 and R 4 Each independently is preferably a hydrogen atom or a hydrocarbon group having 1 to 7 carbon atoms, more preferably a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, and still more preferably a hydrogen atom or a hydrocarbon group having 1 carbon atom.

[0076] n and m are each 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.

[0077] The processing aid disclosed herein preferably includes a synergist, which is at least one selected from the group consisting of polyols having a melting point of 80°C or less, polycaprolactone, silicone, and polyamide-polyether block copolymers. More preferably, the synergist includes at least one selected from the group consisting of polyols having a melting point of 80°C or less and polycaprolactone. This improves processability even further. Furthermore, the aforementioned polyols are preferred as synergists due to their superior processability-improving effects.

[0078] The melting point of the polyol may be 80°C or lower, preferably 75°C or lower, more preferably 70°C or lower, and even more preferably 68°C or lower. It is preferably 10°C or higher, more preferably 20°C or higher, and even more preferably 25°C or higher. Within this range, the effect of improving processability is greater.

[0079] The above polyols can be prepared, for example, from A[(OR 11 ) x2 OR 12 ] y2 In the formula, A is usually an alkylene group having one or more ether bonds, y2 is 2 or 3, (OR 11 ) x2 is an OR having multiple (x2) as oxyalkylene groups 11 The poly(oxyalkylene) chain, R 11 Each independently represents a C2 to C5 alkylene group, and in some embodiments, a C2 to C3 alkylene group, R 12 is hydrogen, alkyl, aryl, arylalkenyl, alkylarylene, -C(O)-alkyl, -C(O)-aryl, -C(O)-arylalkenyl or -C(O)-alkylarylene, -C(O)- and OR 12 O bonding. x2 is 10 to 230,000.

[0080] The above polyol can be R 11 -CH2CH2- or poly (oxypropylene), R 11 They are homopolymers such as poly(ethylene oxide) of -C3H6-.

[0081] The polyols may also be chains of randomly distributed oxyalkylene groups (e.g., -OC2H4- and -OC3H6- units as a copolymer) or chains having alternating blocks of repeating oxyalkylene groups (e.g., containing (-OC2H4-) a1 Block and (-OC3H6-) b1 Block polymer, a1+b1 is 10 to 230,000) chain.

[0082] In some embodiments of the polyols described above, A is ethylene, -CH2-CH(-)-CH2- (derived from glycerol), CH3CH2C(CH2-)3 (derived from 1,1,1-trimethylolpropane), poly(oxypropylene), -CH2CH2-O-CH2CH2- or -CH2CH2-O-CH2CH2-O-CH2CH2-, R 12 is hydrogen, methyl, butyl, phenyl, benzyl, acetyl, benzoyl or stearyl.

[0083] The above-mentioned polyol can be in the following forms: a dicarboxylic acid and a 11 ) x2 OR 12 ] y2 The polyesters prepared from the poly(oxyalkylene) polymers shown, A, R 11 and x2 are defined as above, R 12 is hydrogen, and y2 is 2.

[0084] The above-mentioned polyols may be used alone or in combination of two or more. Polyethylene glycol and polyethylene oxide are preferred, and polyethylene glycol is particularly preferred, from the viewpoint of excellent processability-improving effects.

[0085] 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. Within the above range, the processability is improved more effectively.

[0086] In this specification, the number average molecular weight is calculated from the hydroxyl value measured in accordance with JIS K0070.

[0087] 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 this range, the processability is improved more effectively.

[0088] In this specification, the viscosity average molecular weight is calculated as follows.

[0089] The specific viscosity ηsp of aqueous solutions of various polymer concentrations c (g / dl) in pure water was measured at 35°C using an Ostwald viscometer. 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] was calculated by extrapolating the polymer concentration c to 0. Substituting [η] into the following formula calculated the viscosity-average molecular weight M.

[0090] Formula: [η] = 6.4 × 10 -5 M 0.82

[0091] The polycaprolactone may be a homopolymer of ε-caprolactone or a modified polycaprolactone. Examples of the modified polycaprolactone include polycaprolactone modified by ring-opening polymerization of ε-caprolactone with 1,4-butanediol or the like, and polycaprolactone whose polymer terminals are modified with ether or ester groups.

[0092] 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 range, the processability is improved more effectively.

[0093] In this specification, the weight average molecular weight is measured in terms of polystyrene by gel permeation chromatography (GPC).

[0094] The melting point of the polycaprolactone is preferably 80°C or lower, more preferably 75°C or lower, even more preferably 70°C or lower, and even more preferably 68°C or lower. It is preferably 10°C or higher, more preferably 20°C or higher, and even more preferably 45°C or higher. Within this range, the effect of improving processability is greater.

[0095] In principle, the aforementioned silicones are all organosilicon compounds known to those skilled in the art under the term silicone polymers. A suitable definition of silicones is given in Winnacker / Kuchler: "Chemische Technik" [Chemical Technology], R. Dittmeyer, W. Keim, G. Kreysa, A. Oberholz (eds.), Volume 5: "Organische Zwischenverbindungen, Polymers" [Organic Intermediates, Polymers], Chapter: "Silicones", Wiley-VCH, Weinheim, 2005.

[0096] Silicones can be substituted or unsubstituted linear oligomers or polydiorganosiloxanes, branched silicone polymers, organosilicon resins, or cross-linked silicone polymers. Of course, mixtures of various silicone polymers can be used. As mentioned above, silicone-containing copolymers, such as polyether-functional silicones, silicones containing urea or urethane units, or silicone block copolymers with organic polymers, can also be used. For better compatibility, high molecular weight polydiorganosiloxanes, which may also contain fillers such as microparticulate silicic acid, chalk, talc, and sheet silicates, are particularly preferred.

[0097] Preferably the silicone polymer is equivalent 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, d2 each mean 0 or an integer, a2+b2+c2+d2 is an integer from 5 to 15,000.

[0098] C1 to C18 hydrocarbon residue R 13 Examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, and tert-pentyl residues, hexyl residues such as n-hexyl residues, heptyl residues such as n-heptyl residues, octyl residues such as n-octyl residues and isooctyl residues such as 2,2,4-trimethylpentyl residues, nonyl residues such as n-nonyl residues, decyl residues such as n-decyl residues, cycloalkyl residues such as cyclopentyl residues, cyclohexyl residues, 4-ethylcyclohexyl residues, and cycloheptyl residues, norbornyl residues, and methylcyclohexyl residues. Among the alkyl residues, C1 to C6 residues such as methyl and ethyl residues are preferred, and methyl residues are particularly preferred.

[0099] In addition, R 13Examples of R are unsaturated C1 to C18 hydrocarbon residues such as alkenyl residues, for example, vinyl residues, 2-propen-2-yl residues, allyl residues, 3-buten-1-yl residues, 5-hexen-1-yl residues, 10-undecen-1-yl residues, and cycloalkenyl residues (2-cyclohexenyl residues, 3-cyclohexenyl residues, cyclopentadienyl residues, 2-(cyclohexa-3-en-1-yl)ethyl) residues; aryl residues such as phenyl residues, biphenyl residues, and naphthyl residues; alkylaryl residues such as o-, m-, and p-tolyl residues and phenylethyl residues (2-phenylethyl residues, 1-phenylethyl residues), and aralkyl residues such as benzyl residues. Preferred unsaturated C1 to C18 hydrocarbon residues R 13 are vinyl residues and phenyl residues.

[0100] As the residue R 13 Examples of the substituted hydrocarbon residue are halogenated hydrocarbons such as chloromethyl residue, 3-chloropropyl residue, 3-bromopropyl residue, 3,3,3-trifluoropropyl residue and 5,5,5,4,4,3,3-heptafluoropentyl residue, as well as chlorophenyl residue, dichlorophenyl residue and trifluoromethylphenyl residue.

[0101] Residue R 13 It is preferably bonded to the silicone polymer represented by Formula A via a Si—C bond, but may also be bonded to the silicone polymer via an oxygen atom —O—.

[0102] R 13 It preferably has 1 to 6 carbon atoms. Particularly preferred are ethyl residues, phenyl residues, vinyl residues and methyl residues.

[0103] Preferably, a2+b2+c2+d2 is a number of at least 10, more preferably at least 100, particularly preferably at least 1000 and at most 15000, further preferably at most 10000, particularly preferably at most 7000.

[0104] Preferably, c2+d2 means <0.1×(a2+b2+c2+d2), in particular c2+d2<0.05×(a2+b2+c2+d2).

[0105] Preferably all residues R 13 At least 50%, more preferably at least 70%, particularly preferably at least 80% of the residues are methyl residues.

[0106] In principle, all silicone polymers corresponding to formula A can be used. However, preference is given to silicone polymers having a dynamic viscosity of greater than 1000 mPa·s, as determined using an Anton Paar "MCR 302" rheometer, preferably in accordance with DIN EN ISO 3219:1994 and DIN 53019, using a plate-cone system (cone CP50-2) with an opening angle of 2° and a diameter of 50 mm, a measuring temperature of 25.00° C.±0.05° C., a shear rate of 1 sec·s.

[0107] Among silicones, silicone polymers having very high molecular weights such as UHMW polysiloxane (ultra-high molecular weight; described in KJ Ryan et al., Journal of Vinyl & Additive Technology, March 2000, Vol. 6, No. 1, pp. 7-19) can be used.

[0108] The degree of polymerization of UHMW polysiloxanes ranges from >1000 to about 14,000, which corresponds to a number average molecular weight between 74 kg / mole and 1000 kg / mole.

[0109] Typical UHMW polysiloxanes preferably have a dynamic viscosity of between 10 kPa.s and 50 kPa.s, preferably between 15 kPa.s and 30 kPa.s, measured in accordance with DIN EN ISO 3219:1994 and DIN 53019 using an air flotation rotational rheometer, using a plate-plate system (25 mm diameter) with a measuring gap of 0.5 mm. The measuring temperature is 25.00° C. + / - 0.1° C. The shear rate gradient is 0.1 s- 1 The viscosity reported represents the arithmetic mean of three individual measurements made independently.

[0110] From the perspective of low cost and effectiveness, among the above-mentioned UHMW polysiloxanes, high molecular weight polydimethylsiloxanes having a dynamic viscosity between 1 kPa.s and 50 kPa.s, preferably between 10 and 40 kPa.s, and particularly preferably between 15 and 30 kPa.s (preferably measured by the above-mentioned method) are particularly preferred.

[0111] 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, GENIOPLAST (registered trademark) PELLET S, GENIOPLAST (registered trademark) PELLET P Plus, GENIOPLAST (registered trademark) PE50S08, and GENIOPLAST (registered trademark) PP50S12 manufactured by Asahi Kasei Wacker Silicones, and mixtures thereof. MB50-002 and GENIOPLAST (registered trademark) PELLET S are preferred.

[0112] Silicone polymers are commercially available so that pellets / granules or masterbatches can be used immediately, for example, and can be mixed into thermoplastic granules before further processing them.

[0113] The polyamide-polyether block copolymers described above are copolymers having polyamide blocks and polyether blocks within their polymer backbone. In this disclosure, such block copolymers having polyamide blocks and polyether blocks may also be referred to as "polyamide / polyether block copolymers." Alternatively, they may be abbreviated as "PEBA copolymers" or "PEBA."

[0114] In some embodiments of the present disclosure, the PEBA copolymer may be represented by the following general formula.

[0115] [Chemistry 1]

[0116]

[0117] Here, PA represents a polyamide block, PE represents a polyether block, p represents the length of the PEBA copolymer, and represents the total number of polyamide and polyether blocks. In some embodiments of the present disclosure, the PEBA copolymer can be represented by the following general formula.

[0118] [Chemistry 2]

[0119]

[0120] Here, EG is the first unspecified terminal group, B is an unspecified crosslinking group, and EG * For the second unspecified terminal group, EG, B and EG * Determined by the synthesis method used to produce the PEBA copolymer. Here, n2 represents the length of the polyamide block, x3 represents the length of the amide component within the polyamide block, m1 represents the length of the poly(ether) block, y3 represents the length of the ether component within the poly(ether) block, and p represents the length of the PEBA copolymer, which represents the total number of polyamide and polyether blocks.

[0121] In some embodiments of the present disclosure, the PEBA copolymer may be represented by the following general formula.

[0122] [Chemistry 3]

[0123]

[0124] Here, n2 represents the length of the polyamide block, x3 represents the length of the amide component in the polyamide block, m1 represents the length of the poly(ether) block, y3 represents the length of the ether component in the poly(ether) block, p represents the length of the PEBA copolymer, and represents the total number of polyamide and polyether blocks.

[0125] The polyamide blocks in the above PEBA copolymers are derived from polyamide-12 (PA-12), polyamide-11 (PA-11), polyamide-6 (PA-6) or polyamide-66 (PA-66).

[0126] The weight average molecular weight (eg, Mw and Mn) of the PEBA copolymer can be determined, for example, by gel permeation chromatography (ie, size exclusion chromatography) with narrow molecular weight polymer standards using techniques well known in the art.

[0127] In embodiments, the polyamide blocks in the PEBA copolymer have a number average molecular weight Mn of about 100 to about 15,000 g / mol, or about 300 to about 15,000 g / mol, or about 600 to about 10,000 g / mol, or about 600 to about 5,000 g / mol.

[0128] The polyether blocks in the PEBA copolymers described above have a number average molecular weight, Mn, of about 100 to about 15,000 g / mol, about 100 to about 10,000 g / mol, about 100 to about 6,000 g / mol, about 100 to about 3,000 g / mol, about 200 to about 6,000 g / mol, about 200 to about 3,000 g / mol, about 250 to about 2,000 g / mol, about 750 to about 3,500 g / mol, or about 1,000 to about 3,000 g / mol.

[0129] The number average molecular weight Mn of the PEBA copolymers described above, including subranges therein and any number therein, is from 10,000 to 500,000 g / mol. For example, in embodiments of the present disclosure, the PEBA copolymer has a number average molecular weight, Mn, of 10,000 to 400,000 g / mol, or 10,000 to 300,000 g / mol, 10,000 to 250,000 g / mol, or 15,000 to 300,000 g / mol, or 20,000 to 300,000 g / mol, or 15,000 to 200,000 g / mol, or 20,000 to 200,000 g / mol, or 30,000 to 250,000 g / mol, or about 25,000 to about 75,000 g / mol, or about 50,000 to about 75,000 g / mol, or about 100,000 to about 150,000 g / mol.

[0130] The PEBA copolymers have 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.

[0131] In embodiments, the PEBA copolymer has a weight average molecular weight (Mw), including subranges therein and any number therein, of 25,000 to 500,000 g / mol. For example, in embodiments of the present disclosure, the PEBA copolymer has a weight average molecular weight (Mw) of about 100,000 to about 250,000 g / mol, or about 100,000 to about 150,000 g / mol, or about 125,000 to about 150,000 g / mol.

[0132] The polyamide and polyether blocks within the above-mentioned PEBA copolymers may be randomly distributed.

[0133] The PEBA copolymer comprises polyamide blocks and polyether blocks, with the polyamide blocks constituting at least 50% by mass of the copolymer. The PEBA copolymer comprises polyamide blocks and polyether blocks, with the polyether blocks constituting at least 50% by mass of the copolymer. Furthermore, the PEBA copolymer comprises polyamide blocks and polyether blocks, and the molar ratio of the polyamide blocks to the polyether blocks may be in the range of 1:3 to 3:1, 1:2 to 2:1, 3:2 to 1:3, 2:3 to 3:1, or approximately 1:1.

[0134] PEBA copolymers having polyamide and polyether blocks can be prepared by reacting the polyamide and polyether block precursors described above. For example, reacting a lactam, a polyether diol, and a chain-limiting diacid in the presence of a small amount of water can yield PEBA copolymers having polyamide and polyether blocks of variable length and a statistically random distribution within the block copolymer chain.

[0135] The polyether blocks are derived from poly(ethylene oxide), poly(propylene oxide), or poly(tetramethylene ether) glycol, each of which can be co-condensed with polyamide blocks containing carboxylic acid chain ends. The presence of a chain limiter during the polycondensation reaction can provide PEBA copolymers containing polyamide and polyether blocks randomly distributed within the block copolymer.

[0136] The polyether blocks are derived from poly(ethylene oxide), poly(propylene oxide), or poly(tetramethylene ether) glycols, which are initially converted to polyether diamines through amination and then co-condensed with polyamide blocks containing carboxylic acid chain ends. The presence of a chain limiter during the polycondensation reaction provides a PEBA copolymer containing polyamide and polyether blocks randomly distributed within the block copolymer.

[0137] The polyether blocks described above may be derived from poly(ethylene oxide), also known as polyethylene glycol (PEG).

[0138] The polyether blocks described above may be derived from poly(oxypropylene), also known as polypropylene glycol (PPG).

[0139] The polyether blocks described above may be extended from poly(tetramethylene ether) glycol (PTMG), also known as polytetramethylene oxide (PTMEO) or polytetrahydrofuran (PTHF).

[0140] 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.

[0141] 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). In one embodiment of the present disclosure, the PEBA copolymer comprises i) a polyamide block selected from polyamide-12 (PA-12), and ii) a polyether block selected from polyethylene glycol (PEG).

[0142] The PEBA copolymer comprises 10 to 20 polyamide blocks and 10 to 20 polyether blocks.

[0143] The above-mentioned PEBA copolymers contain only one polyamide block and one polyether block.

[0144] The PEBA copolymer comprises i) a polyamide block which is polyamide-12 (PA-12) and ii) a polyether block which is polyethylene glycol (PEG), wherein the polyamide-12 block accounts for approximately 30% to 70% by mass of the copolymer, and the polyethylene glycol block accounts for approximately 70% to 30% by mass of the copolymer.

[0145] The PEBA copolymer comprises i) a polyamide block which is polyamide-12 (PA-12) and ii) a polyether block which is polyethylene glycol (PEG), wherein the polyamide-12 block accounts for approximately 40% to 60% by mass of the copolymer, and the polyethylene glycol block accounts for approximately 60% to 40% by mass of the copolymer.

[0146] The PEBA copolymer comprises i) polyamide blocks as polyamide-12 (PA-12) and ii) polyether blocks as polyethylene glycol (PEG), wherein the polyamide-12 blocks account for about 45% by mass of the copolymer and the polyethylene glycol blocks account for about 55% by mass of the copolymer.

[0147] 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).

[0148] The PEBA copolymer comprises i) a polyamide block as polyamide-12 (PA-12), and ii) a polyether block as polyethylene glycol (PEG), and has a number average molecular weight Mn of about 25,000 to about 75,000 g / mol.

[0149] The PEBA copolymer comprises i) a polyamide block comprising polyamide-12 (PA-12) and ii) a polyether block comprising 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 comprising polyamide-12 (PA-12) and ii) a polyether block comprising polyethylene glycol (PEG), and has a number average molecular weight Mn of about 66,100 g / mol.

[0150] 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 100,000 to about 150,000 g / mol.

[0151] 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 125,000 to about 150,000 g / mol.

[0152] The PEBA copolymer comprises i) a polyamide block as polyamide-12 (PA-12) and ii) a polyether block as polyethylene glycol (PEG), and has a weight average molecular weight Mw of about 134,000 g / mol.

[0153] In one embodiment of the present disclosure, the PEBA copolymer comprises i) a polyamide block which is polyamide-6 (PA-6), and ii) a polyether block which is polyethylene glycol (PEG).

[0154] The PEBA copolymer comprises i) a polyamide block as polyamide-6 (PA-6) and ii) a polyether block as polyethylene glycol (PEG), wherein the polyamide-6 block accounts for about 30% to 60% by mass of the copolymer and the polyethylene glycol block accounts for about 70% to 40% by mass of the copolymer.

[0155] The PEBA copolymer comprises i) a polyamide block as polyamide-6 (PA-6) and ii) a polyether block as polyethylene glycol (PEG), wherein the polyamide-6 block accounts for about 50% to 35% by mass of the copolymer and the polyethylene glycol block accounts for about 50% to 65% by mass of the copolymer.

[0156] The above PEBA copolymer comprises i) 10 to 20 polyamide blocks as polyamide-6 (PA-6), and ii) 10 to 20 polyether blocks as polyethylene glycol (PEG).

[0157] The PEBA copolymer comprises i) a polyamide block comprising polyamide-11 (PA-11) and ii) a polyether block comprising polyethylene glycol (PEG). In one embodiment of the present disclosure, the PEBA copolymer comprises i) a polyamide block comprising polyamide-12 (PA-12) and ii) a polyether block comprising polytetrahydrofuran (PTHF).

[0158] The PEBA copolymer comprises i) a polyamide block which is polyamide-12 (PA-12), and ii) a polyether block which is polytetramethyleneimine (PTHF), wherein the polyamide-12 block accounts for about 75% to 10% by mass of the copolymer, and the polytetramethyleneimine block accounts for about 25% to 90% by mass of the copolymer.

[0159] The PEBA copolymer comprises i) a polyamide block which is polyamide-12 (PA-12), and ii) a polyether block which is polytetramethyleneimine (PTHF), wherein the polyamide-12 block accounts for about 80% to 60% by weight of the copolymer, and the polytetramethyleneimine block accounts for about 20% to 40% by weight of the copolymer.

[0160] The PEBA copolymer comprises i) a polyamide block which is polyamide-12 (PA-12), and ii) a polyether block which is polytetramethyleneimine (PTHF), wherein the polyamide-12 block accounts for about 40% to 60% by mass of the copolymer, and the polytetramethyleneimine block accounts for about 60% to 40% by mass of the copolymer.

[0161] The PEBA copolymer comprises i) a polyamide block which is polyamide-12 (PA-12), and ii) a polyether block which is polytetramethyleneimine (PTHF), wherein the polyamide-12 block accounts for about 30% to 10% by mass of the copolymer, and the polytetramethyleneimine block accounts for about 70% to 90% by mass of the copolymer.

[0162] The above PEBA copolymer comprises i) 10 to 20 polyamide blocks as polyamide-12 (PA-12), and ii) 10 to 20 polyether blocks as polytetrahydrofuran (PTHF).

[0163] The PEBA copolymer comprises i) a polyamide block as polyamide-12 (PA-12) and ii) a polyether block as polytetrahydrofuran (PTHF), and has a number average molecular weight Mn of about 25,000 to about 75,000 g / mol.

[0164] The PEBA copolymer comprises i) a polyamide block comprising polyamide-12 (PA-12) and ii) a polyether block comprising polytetramethyleneimine (PTHF), and has a number average molecular weight (Mn) of about 40,000 to about 60,000 g / mol. In embodiments of the present disclosure, the PEBA copolymer comprises i) a polyamide block comprising polyamide-12 (PA-12) and ii) a polyether block comprising polytetramethyleneimine (PTHF), and has a number average molecular weight (Mn) of about 50,000 g / mol.

[0165] The above-mentioned PEBA copolymer comprises i) a polyamide block which is polyamide-6 (PA-6), and ii) a polyether block which is polytetrahydrofuran (PTHF).

[0166] The above-mentioned PEBA copolymer comprises i) a polyamide block which is polyamide-11 (PA-11), and ii) a polyether block which is polytetrahydrofuran (PTHF).

[0167] The PEBA copolymer is a commercially available elastomer, and is sold under the trade name of PEBAX (registered trademark).

[0168] 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, PEBAX4033 SP01, PEBAX 4533 SA 01, PEBAX 4533 SA 01 MED, PEBAX 4533 SP01, PEBAX 5513 SA01, PEBAX 5513 SP01, PEBAX 5533 SA 01, PEBAX 5533 SA 01 MED, PEBAX 5533 SN 70BLACK,PEBAX 5533 SP01,PEBAX SA 01,PEBAX 6333 SA 01 MED,PEBAX SP01,PEBAX 6333SP01,PEBAX 6333 SA 01,PEBAX,PEBAX 3533 SA 01,PEBAX 3533 SA 01 MED,PEBAX 3533SP01,PEBAX 4011 SA 01,PEBAX 4033 SA 01 MED,PEBAX 4033 SP01,PEBAX 4033SA 01MED,PEBAX Clear 2533,PEBAX ES 2533 UV,PEBAX MH 2533,PEBAX MH2030,PEBAX MV5513 SA 01,PEBAX MV 5513 SA 01 MED, PEBAX MV 5533 SP01, PEBAX MV 5533, PEBAX MV5533 SP01, PEBAX RNEW (registered trademark) 30R51 SA 01, PEBAX RNEW 35R53 SP01, PEBAX RNEW 70R53 SP01, PEBAX RNEW 55R53 SP01, PEBAX RNEW 63R53 SP01, PEBAX RNEW 70R53 SP01, PEBAX RNEW 70R53 SP01, PEBAX, PEBAX RNEW 72R53 SP01, PEBAX RNEW 80R53 SP 02 and mixtures thereof

[0169] The PEBA copolymer is a commercially available elastomer sold under the trade name VESTAMID (registered trademark) or VESTAMID E.

[0170] 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 them, Pebax MV1072 is preferred.

[0171] The PEBA copolymers can be used in the form of a semi-solid or viscous liquid, or as a powder, pellets or granules.

[0172] In the processing aid disclosed herein, the content of the synergist is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1% by mass or more, and is preferably 40% by mass or less, more preferably 30% by mass or less, and even more preferably 20% by mass or less.

[0173] In the processing aid disclosed herein, the mass ratio of the biodegradable polymer to 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 disclosed herein does not contain 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.

[0174] In the processing aid disclosed herein, the total content of the biodegradable polymer and the synergist is preferably 70% by mass or more, more preferably 80% by mass or more, further 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.

[0175] The processing aid disclosed herein may contain components other than the above-mentioned biodegradable polymer and the above-mentioned synergist.

[0176] The processing aid disclosed herein preferably comprises ethylene-vinyl alcohol copolymer, thereby achieving a better improvement in processability.

[0177] 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, and 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, and even more preferably 10 g / 10 min or less. Within this range, the effect of improving processability is further enhanced.

[0178] 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, and more preferably 40 mol% or less. Within the above range, the processability is further improved.

[0179] In this specification, the ethylene content is determined by a nuclear magnetic resonance (NMR) method.

[0180] The ethylene-vinyl alcohol copolymer is preferably obtained by saponifying an ethylene-vinyl ester copolymer, and particularly preferably obtained by saponifying an ethylene-vinyl acetate copolymer.

[0181] The saponification degree of the ethylene-vinyl alcohol copolymer is preferably 80 to 100 mol%.

[0182] When copolymerizing ethylene and vinyl acetate, other fatty acid vinyl esters (vinyl propionate, vinyl pivalate, etc.) may also be used in combination. In addition, the ethylene-vinyl alcohol copolymer may also contain 0.0002 to 0.2 mol% of a vinylsilane compound as a copolymerization component. Here, examples of the vinylsilane compound include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri(β-methoxy-ethoxy)silane, and γ-methacryloyloxypropylmethoxysilane. Among them, vinyltrimethoxysilane and vinyltriethoxysilane are preferably used.

[0183] When ethylene and vinyl acetate are copolymerized, monomers other than the above-mentioned fatty acid vinyl esters and vinyl silane compounds may also coexist in small amounts, 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 monoalkyl esters 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 ketone, N-vinyl pyrrolidone, vinyl chloride, and vinylidene chloride.

[0184] In the ethylene-vinyl alcohol copolymer, the content of polymerized units derived from 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%.

[0185] In this specification, the content of polymerization units based on monomers other than ethylene and vinyl alcohol is determined by a nuclear magnetic resonance (NMR) method.

[0186] In the processing aid disclosed herein, the content of the ethylene-vinyl alcohol copolymer is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1% by mass or more, and is preferably 90% by mass or less, more preferably 70% by mass or less, and even more preferably 50% by mass or less.

[0187] In the processing aid disclosed herein, 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.

[0188] In the processing aid disclosed herein, 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.

[0189] In the processing aid disclosed herein, 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 100% by mass.

[0190] The processing aid of the present disclosure preferably comprises a lubricant (A).

[0191] The lubricant (A) is an additive that reduces friction and improves sliding properties, and examples thereof include waxes, alcohols, surfactants, etc. These may be used alone or in combination of two or more.

[0192] The lubricant (A) is preferably at least one selected from the group consisting of waxes, alcohols, and surfactants.

[0193] Examples of the waxes include pure hydrocarbon waxes such as liquid paraffin, natural paraffin, microcrystalline wax, synthetic paraffin, polyethylene wax, and polyethylene / polypropylene wax; fatty acid waxes such as higher fatty acids and oxygen-containing fatty acids; fatty amide waxes such as fatty amides and bis-fatty amides; and fatty acid ester waxes such as lower alcohol esters of fatty acids, polyol esters of fatty acids such as glycerides, polyethylene glycol esters of fatty acids, and fatty alcohol esters of fatty acids (ester waxes). Of these, pure hydrocarbon waxes or fatty acid ester waxes are preferred. Preferred pure hydrocarbon waxes are polyethylene wax and polyethylene / polypropylene wax, and preferred fatty acid ester waxes are adipic acid esters or glycerol fatty acid esters.

[0194] Examples of fatty acid ester waxes include phthalates, dimethyl and diethyl succinates and related esters, monoacetin, diacetin, triacetin, monoglycerides, citrates, adipates, stearates, and oleates. These may be used alone or in combination.

[0195] Examples of the adipate include adipic acid diesters. Specifically, dimethyl adipate, dibutyl adipate, bis[2-(2-methoxyethoxy)ethyl]adipate, bis(diethylene glycol butyl ether) adipate, bis(methyldiglycol) adipate, benzyl[2-(2-methoxyethoxy)ethyl]adipate, di-n-butyl adipate, dioctyl adipate, methyldiglycol diethylene glycol butyl ether adipate, benzyl glycol monomethyl ether adipate, benzyl diethylene glycol butyl ether adipate, and diisononyl phthalate. These may be one or more. Among them, diisononyl phthalate or dioctyl adipate is preferred.

[0196] As glyceryl fatty acid ester, can enumerate glyceryl monostearate, glyceryl monobehenate, single 12-hydroxystearic acid glyceryl ester, glyceryl monooleate, glyceryl monocaprylate, glyceryl monocaprate, glyceryl monolaurate, diacetyl monolaurate glyceryl, succinic acid fatty acid monoglyceride, citric acid fatty acid monoglyceride, diacetyl tartaric acid fatty acid monoglyceride, diglyceryl laurate, diglyceryl stearate, diglyceryl oleate, diglyceryl monolaurate, diglyceryl monomyristic acid, diglyceryl monostearate, diglyceryl monooleate, tetraglyceryl stearate, decaglycerol laurate, decaglycerol stearate, decaglycerol oleate, polyglycerol polyricinoleate, propylene glycol monolaurate, propylene glycol monopalmitate, propylene glycol monostearate, propylene glycol monooleate, propylene glycol monobehenate etc.These can be only 1 kind, also can be 2 or more kinds.Wherein, preferred diacetyl monolaurate glyceryl or decaglycerol stearate.

[0197] Examples of the alcohols include aliphatic alcohols such as higher alcohols; and polyols such as polyglycols and polyglycerols.

[0198] Examples of the fatty alcohol include lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol, and behenyl alcohol, etc. These may be used alone or in combination of two or more.

[0199] 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 esters, ethers, ester / ethers, and amides; and amphoteric surfactants such as aminocarboxylates, alkyl betaines, and alkyl imidazoline derivatives. Of these, anionic surfactants or nonionic surfactants are preferred. Anionic surfactants are preferably metal soaps, specifically carboxylates, sulfates, sulfonates, and phosphates. Nonionic surfactants are preferably ester / ethers, specifically sugar-based surfactants.

[0200] Examples of the metal soap include fatty acid salts, polysulfone salts, polycarboxylates, alkyl sulfates, alkyl aryl sulfonates, alkyl naphthalene sulfonates, dialkyl sulfonates, dialkyl sulfosuccinates, alkyl phosphates, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkyl aryl ether sulfates, and polyoxyethylene alkyl phosphate sulfonates. Specific examples include sodium dodecylbenzenesulfonate, sodium lauryl sulfate, sodium polyoxyethylene lauryl ether sulfate, and polyoxyethylene nonylphenyl ether sulfate. These may be one or more.

[0201] The metal soap is preferably a compound represented by the following general formula (1), for example.

[0202] (R 5 COO) n1 M1 (1)

[0203] (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 in the range of 1 to 4, M 1 (e.g., 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 a rare earth element.)

[0204] In the above general formula (1), when n1 is an integer greater than 2, two or more R 5 They can be the same as or different from each other.

[0205] R 5 The alkyl group having 1 to 21 carbon atoms may be a linear alkyl group or a branched alkyl group, and may contain an alicyclic structure.

[0206] R 5 The alkyl group having 1 to 21 carbon atoms corresponds to the R 5 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 an acetic acid residue, a propionic acid residue, a butyric acid residue, a valeric acid residue, an acrylic acid residue, a methacrylic acid residue, an octanoic acid residue (2-ethylhexanoic acid residue), a neodecanoic acid residue, a cyclohexaneic acid residue, an isononanoic acid residue, an eleostearic acid residue, a tall oil fatty acid residue, a coconut oil fatty acid residue, a soybean oil fatty acid residue, a linseed oil fatty acid residue, a safflower oil fatty acid residue, a dehydrated castor oil fatty acid residue, a tung oil fatty acid residue, a lauric acid residue, a myristic acid residue, a palmitic acid residue, a stearic acid residue, an isostearic acid residue, an oleic acid residue, and a 12-hydroxystearic acid residue.

[0207] From the perspective of improving processability, R 5 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 still more preferably a stearic acid residue or a 12-hydroxystearic acid residue.

[0208] 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.

[0209] n1 is the number of cells that are connected by M 1 The value determined by the ionic valence of the metal atom, such as M 1 When it is boron, n1 is 3, M 1 When it is cobalt, n1 is 2.

[0210] The metal soap also includes a fatty acid borate metal salt. The fatty acid borate metal salt is, for example, a compound represented by the following general formula (2).

[0211] (R 6 COO-M 2 -O)3B (2)

[0212] (In the above general formula (2), R 6 is a hydrogen atom or an alkyl group having 1 to 21 carbon atoms, 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.)

[0213] In the above general formula (2), R 6 The alkyl group having 1 to 21 carbon atoms and R 5 The alkyl groups having 1 to 21 carbon atoms are the same. Similarly, in the above general formula (2), M 2 The metal and M of the above general formula (1) 1 The same metal.

[0214] The above-mentioned metal soap may be used alone or in combination of two or more metal soaps having different structures.

[0215] 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.

[0216] In addition, examples of the metal constituting the metal salt include zinc, magnesium, and calcium, 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 can be used.

[0217] Examples of the ammonium salt-based anionic surfactants include fatty acid ammonium salts, for example, ammonium lauryl sulfate, and polyoxyethylene lauryl ether sulfate. The anionic surfactant may be used alone or in combination of two or more.

[0218] Examples of the cationic surfactant include alkylamine salts and quaternary ammonium salts. Specifically, examples include stearylamine acetate, cocotrimonium chloride, tallowtrimethylammonium chloride, dimethyldioleylammonium chloride, methyloleyldiethanol chloride, tetramethylammonium chloride, laurylpyridinium chloride, laurylpyridinium bromide, laurylpyridinium disulfate, cetyltrimethylammonium chloride, cetylpyridinium bromide, 4-alkylmercaptopyridine, poly(vinylpyridine)-dodecyl bromide, and dodecylbenzyltriethylammonium chloride. The cationic surfactant may be one or more.

[0219] Examples of the amphoteric surfactant include aminocarboxylates, alkyl betaine-type surfactants, and alkyl imidazoline derivatives, and specifically, lauramide propyl betaine. The amphoteric surfactant may be used alone or in combination of two or more.

[0220] Examples of the ether-type nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyalkylene derivatives, polyoxyethylene phenyl ethers, and alkyl allyl ethers. Specific examples include polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, and polyoxyethylene octylphenyl ether.

[0221] Examples of the ester / ether type nonionic surfactant include sugar-type surfactants, specifically sorbitan fatty acid esters, sorbitol, and polyoxyethylene sorbitan fatty acid esters.

[0222] The nonionic surfactant may be used alone or in combination of two or more.

[0223] Examples of the sugar-type surfactant include sucrose fatty acid esters, sorbitan esters, and polysorbates.

[0224] Specific examples of the sugar-type surfactants 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 octanoate, sorbitan dioleate, sorbitan distearate, sorbitan stearate, sorbitan sesqui ... Sorbitan isostearate, sorbitan sesquioleate, sorbitan sesquioctanoate, sorbitan sesquistearate, sorbitan triisostearate, sorbitan trioleate, sorbitan tristearate, sorbitan palmitate, coconut oil fatty acid sorbitan, sorbitan laurate, olive fatty acid sorbitan, and other sorbitan fatty acid esters; sucrose isobutyrate acetate, sucrose octaacetate, sucrose oleate , Distearate sucrose, Dilaurate sucrose, Stearate sucrose, Tetraisostearate sucrose, Tetrahydroxystearate sucrose, Tristearate sucrose, Tribehenate sucrose, Trilaurate sucrose, Triacetate sucrose, Palmitate sucrose, Hexaerucate sucrose, Hexapalmitate sucrose, Pentaerucate sucrose, Pentahydroxystearate sucrose, Polyoleate sucrose, Polystearate sucrose, Polysoybean oil fatty acid sucrose, Polypalmitate fatty acid sucrose, Polybehenate sucrose , polylaurate sucrose, polylinoleate sucrose, polycotton fatty acid sucrose, myristic acid sucrose, coconut oil fatty acid sucrose, laurate sucrose, ricinoleate sucrose, benzoate sucrose, distearate sucrose acetate, stearate sucrose acetate and other sucrose fatty acid esters; coconut oil fatty acid glucoside, lauryl glucoside, decyl glucoside, myristyl glucoside, palmityl glucoside, stearyl glucoside and coconut glucoside and other alkyl glucosides. These can be used alone or in combination of two or more.

[0225] As the sugar-type surfactant, sorbitan esters containing a nonpolar carboxylic acid (lipophilic group) bonded to a polar sorbitan group (hydrophilic group) via an ester bond are preferred. Polyoxyethylene derivatives of sorbitan esters and polyoxyethylene oligomers chemically substituted with two or more groups on the sorbitan group are also preferred.

[0226] These polyoxyethylene derivatives of sorbitan esters are called polysorbates.

[0227] Specifically, the polyoxyethylene derivatives of sorbitan esters (also known as polysorbates) are of formula (I):

[0228] [Chemistry 4]

[0229]

[0230] Here, R 7 ~R 10 One of them is a straight chain fatty acid part, R 7 ~R 10The other three of them are hydrogen respectively.

[0231] In addition, w1, x1, y1, and 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.

[0232] In addition, the linear fatty acid part is preferably of the formula (C=O)(CH2) a CH3.

[0233] The fatty acid part may alternatively contain double bonds along the hydrocarbon chain (i.e., may contain monovalent unsaturation), such that the formula is (C=O)(CH2) b (CH)=(CH)(CH2) c CH3.

[0234] 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.

[0235] In addition, b + c is an integer between 8 and 23, preferably an integer from 10 to 18.

[0236] The number of unsaturated bonds in the hydrocarbon chain may contain two or more unsaturations. The unsaturation is preferably 4 or less, more preferably 3 or less, and particularly preferably maintained at 0, 1, or 2.

[0237] As specific examples of polysorbates, 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) can be cited.

[0238] The 20, 40, 60, and 80 after "polysorbate" represent the fatty acid part (the "lipophilic group" of the molecule) added to the polyoxyethylene sorbitan part (the "hydrophilic group" of the molecule). 20 is monolaurate, 40 is monopalmitate, 60 is monostearate, and 80 is monooleate (an example of a monovalent unsaturated fatty acid part).

[0239] The name "polysorbate #" means that 20 ethylene oxide moieties [-(CH2CH2O)-] are added to sorbitan ester.

[0240] In a specific embodiment, the above sugar-based surfactant may be one or more of polysorbate 20, polysorbate 40, polysorbate 60, and / or polysorbate 80, or may contain one or more of them. For example, the surfactant may be polysorbate 60, or may contain other polysorbates.

[0241] In addition, instead of the above-mentioned polysorbates, surfactants that are variants of the above-mentioned specific polysorbates may be used.

[0242] For example, referring to Formula I, R 7 ~R 10 2, 3 or all of them can be straight chain fatty acid moieties (if R 7 ~R 10 The remainder is hydrogen).

[0243] Examples of such compounds include: R 7 ~R 10 Three of them are fatty acid parts, stearic acid, R 7 ~R 10 The other one is hydrogenated polyoxyethylene sorbitan tristearate.

[0244] In the processing aid disclosed herein, the content of the lubricant (A) is preferably 1% by mass or more, more preferably 2% by mass or more, and even more preferably 4% by mass or more, and is preferably 99% by mass or less, more preferably 60% by mass or less, and even more preferably 40% by mass or less.

[0245] In the processing aid disclosed herein, 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.

[0246] In the processing aid disclosed herein, the mass ratio of the biodegradable polymer to the ethylene-vinyl alcohol copolymer to 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.

[0247] Preferred combinations of the biodegradable polymer, the ethylene-vinyl alcohol copolymer, and the lubricant (A) include combinations of polylactic acid and / or polybutylene succinate as the biodegradable polymer, an ethylene-vinyl alcohol copolymer, and at least one member selected from the group consisting of zinc stearate, magnesium hydroxystearate, and calcium stearate as the lubricant (A). However, combinations other than the above may also be used.

[0248] The processing aid of the present disclosure preferably contains an anti-deterioration agent.

[0249] As the anti-degradation agent, a compound including at least one skeleton selected from the group consisting of a phenol skeleton and a phosphoric acid skeleton can be preferably used.

[0250] When the anti-degradation agent has a phenol skeleton, the number thereof is not particularly limited, but is preferably 1 or more, more preferably 2 or more, further preferably 3 or more, and particularly preferably 4 or more, and is preferably 100 or less, more preferably 10 or less, and further preferably 6 or less.

[0251] Specific examples of the anti-degradation agent having a phenol skeleton include 2,6-di-tert-butyl-p-cresol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-dicyclohexyl-4-methylphenol, 2,6-diisopropyl-4-ethylphenol, 2,6-di-tert-amyl-4-methylphenol, 2,6-di-tert-octyl-4-n-propylphenol, 2,6-dicyclohexyl-4-n-octylphenol, 2-isopropyl-4-methyl-6-tert-butylphenol, 2-tert-butyl-4-ethyl-6-tert-octylphenol, 2-isobutyl-4-ethyl-6-tert-hexylphenol, 2-cyclohexyl-4-n-butyl-6-isopropylphenol, styrenated mixed cresols, DL-α-tocopherol, stearyl β-tocopherol, Compounds with a phenol skeleton (monocyclic phenolic compounds) such as 2,6-di-tert-butyl-4-(4,6-bis(octylthio)-1,3,5-triazin-2-ylamino)phenol; 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 4,4'-butylenebis(3-methyl-6-tert-butylphenol), 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'-thiobis(4-methyl-6-tert-butylphenol), 4,4'-methylenebis(2,6-di-tert-butylphenol), 2,2'-methylenebis[6-(1-methylcyclohexyl)-p-cresol], 2,2'-ethylene ...4,4'-methylenebis(2,6-di-tert-butylphenol), 2,2'-methylenebis[6-(1- Compounds with two phenol skeletons (bicyclic phenol compounds) such as bis(4,6-di-tert-butylphenol), 2,2'-butylenebis(2-tert-butyl-4-methylphenol), 3,6-dioxaoctamethylenebis[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate], triethylene glycol bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], and 2,2'-thiodiethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]; 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, 1,3,5-tris(2 Compounds having three phenol skeletons (tricyclic phenol compounds) such as trimethylol-2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl) isocyanurate, 1,3,5-tris[(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxyethyl] isocyanurate, tris(4-tert-butyl-2,6-dimethyl-3-hydroxybenzyl) isocyanurate, and 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene; compounds having four phenol skeletons (tetracyclic phenol compounds) such as tetrakis[methylene-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]methane and pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], etc.Among them, tetracyclic phenol compounds are preferred, tetrakis[methylene-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]methane and pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] are more preferred, and pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] is further preferred.

[0252] The phosphate skeleton is a skeleton having a structure in which 1 to 4 O (oxygen atoms) are bonded to 1 P (phosphorus atom). Among them, a skeleton in which 3 O (oxygen atoms) are bonded to 1 P (phosphorus atom) is preferred.

[0253] When the anti-degradation agent has a phosphate backbone, the number thereof is not particularly limited, but is preferably 1 or more, more preferably 2 or more, and even more preferably 3 or more, and is preferably 100 or less, more preferably 10 or less, and even more preferably 6 or less.

[0254] Specific examples of the anti-degradation agent having a phosphate skeleton include:

[0255] [Chemistry 5]

[0256]

[0257] (Among them, R 1 is selected from the group consisting of a linear or branched alkyl group and an aryl group having 1 to 16 carbon atoms, R 1 They may be the same or different), and P(OR 1 )3 formula (where R 1 The compound represented by the group consisting of a linear or branched alkyl group having 4 to 32 carbon atoms), more specifically, trilauryl phosphite, triisodecyl phosphite, tridecyl phosphite, trihexadecyl phosphite, trioctadecyl phosphite, tribehenyl phosphite, trieicosyl phosphite, triceryl phosphite, trioleyl phosphite, tris(2-ethylhexyl) phosphite, for example, diphosphates such as monostearyl phosphite (or its tautomer monostearyl phosphonate), distearyl phosphite (distearyl phosphonate), and high molecular weight homologs, partially esterified phosphonic acid compounds, and alkali metal salts, alkaline earth metal salts, aluminum salts or zinc salts thereof.

[0258] Examples of diphosphorous acid include tetraethyl diphosphite and tetrapropyl diphosphite, and examples of triphosphorous acid include P,P'-bis(2-hydroxyethyl) triphosphorous acid.

[0259] Oligomeric phosphites and polyphosphites (oligomers and polymers) are described in, for example, International Publication No. 2011 / 102861, International Publication No. 2014 / 20519, and International Publication No. 2020 / 123986. Compounds described in these international publications can also be used. The following compounds can be cited as examples.

[0260] [Chemistry 6]

[0261]

[0262] In addition, for example, phosphates, diphosphates, metaphosphates, and polyphosphates derived from the above-mentioned phosphites such as trilauryl phosphate, triisodecyl phosphate, tridecyl phosphate, trihexadecyl phosphate, trioctadecyl phosphate, tribehenyl phosphate, trieicosyl phosphate, triceryl phosphate, and trioleyl phosphate, as well as the following structures and salts derived therefrom, and a mixture of at least two phosphates selected from the group consisting of monoalkyl phosphates, dialkyl phosphates, and trialkyl phosphates.

[0263] [Chemistry 7]

[0264]

[0265] In the case of the above-mentioned phosphates, diphosphates, metaphosphates and polyphosphates as the above-mentioned phosphite derivatives, the phosphorus atom exists at an oxidation number of +V, not at an oxidation number of +III as in phosphites.

[0266] As the anti-degradation agent having a phosphoric acid skeleton, phosphites are preferred. Examples of phosphites include the following compounds.

[0267] [Chemistry 8]

[0268]

[0269] [Chemistry 9]

[0270]

[0271] [Chemistry 10]

[0272]

[0273] In addition, as a particularly preferred phosphite, tris(2,4-di-tert-butylphenyl) phosphite can also be mentioned.

[0274] Specific examples of the anti-degradation agent having a phenol skeleton and a phosphate skeleton include phosphorus-containing phenol compounds such as calcium bis(3,5-di-tert-butyl-4-hydroxybenzylphosphonate) and nickel bis(3,5-di-tert-butyl-4-hydroxybenzylphosphonate).

[0275] The anti-degradation agent may have only one of a phenol skeleton and a phosphoric acid skeleton, or may have both a phenol skeleton and a phosphoric acid skeleton uniformly. However, it preferably has only one of a phenol skeleton and a phosphoric acid skeleton.

[0276] The above-mentioned antioxidant is preferably a combination of an antioxidant having only a phenol skeleton (phenolic antioxidant) and an antioxidant having only a phosphate skeleton (phosphoric acid antioxidant). This improves the pressure stability during extrusion.

[0277] When a phenolic antioxidant and a phosphoric acid antioxidant are used in combination as the antioxidant, the mass ratio of these agents (phenolic antioxidant:phosphoric acid antioxidant) 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.

[0278] In the processing aid disclosed herein, the content of the anti-degradation agent is preferably 10% by mass or more, more preferably 30% by mass or more, and even more preferably 40% by mass or more, and is preferably 80% by mass or less, more preferably 70% by mass or less, and even more preferably 60% by mass or less.

[0279] The processing aid disclosed herein is substantially fluorine-free. "Substantially fluorine-free" means that the fluorine content in the processing aid is 10 ppm or less (preferably 1 ppm or less, more preferably 0.1 ppm or less). The processing aid disclosed herein is more preferably fluorine-free (fluorine content is 0% by mass).

[0280] The processing aid disclosed herein can be obtained by, for example, a mixing step of adding the biodegradable polymer to a mixer and mixing the biodegradable polymer, and a discharging step of discharging the mixture from the mixer. The present disclosure also relates to a method for producing the processing aid comprising the mixing and discharging steps.

[0281] The mixing method is not particularly limited and may be mixing (kneading) with or without applying shearing force. Of these, kneading is preferred, and melt kneading is more preferred, in order to effectively exhibit the aforementioned moldability.

[0282] In the case of melt kneading, the components may be melted during the mixing step or may be melted before the mixing step.

[0283] In the above-mentioned production method, a molding step of molding the discharged product using a molding machine or the like may be performed after the discharging step.

[0284] The method of the molding step is not particularly limited, and examples thereof include extrusion molding, injection molding, and blow molding. Among them, extrusion molding is preferred in order to effectively exhibit the above-mentioned molding processability.

[0285] An extruder is used in the extrusion molding. Examples of the extruder include single-screw extruders, twin-screw extruders, and tandem extruders. The extruder typically comprises a barrel, a screw stored within the barrel, a die head mounted at the front end of the barrel, and a feed hopper for supplying pellets to the barrel.

[0286] The various conditions related to the above-mentioned molding are not particularly limited and can be appropriately set according to the composition and amount of the composition, the shape and size of the desired molded article, etc. The form of the processing aid disclosed herein is not particularly limited and can be powder, granules, pellets, etc., but pellets are preferred from the perspectives of excellent handleability and ease of molding.

[0287] The processing aid disclosed herein is particularly useful as a processing aid for thermoplastic resins (particularly polyolefin resins).

[0288] <Masterbatch>

[0289] The masterbatch of the present disclosure includes the processing aid of the present disclosure and a thermoplastic resin (A).

[0290] The processing aid disclosed herein can be directly added to an object such as a thermoplastic resin. By adding it in the form of a masterbatch, metering stability and good dispersibility can be achieved, thereby achieving a better effect of improving processability.

[0291] Examples of the thermoplastic resin (A) include polyolefin polymers (polyethylene (PE)·polypropylene (PP)·ethylene·propylene copolymers), polystyrene (PS), AS (acrylonitrile styrene) resin (AS), ABS (acrylonitrile butadiene styrene) resin (ABS), methacrylic resin (PMMA), polymethylpentene (PMP), butadiene resin (BDR), polybutene-1 (PB-1), polyvinyl alcohol (PVA), polyacrylonitrile (PAN), styrene polymethacrylate (MS), ethylene vinyl acetate copolymer (EVA), ethylene-vinyl alcohol copolymer, and polyvinyl chloride (PVC). 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.

[0292] Among polyolefin polymers, homopolymers (e.g., homopolymers of C2-C10 α-olefins, preferably C2-C6 α-olefins) can be cited. Specific examples of homopolymers include homopolyethylene and polypropylene (hPP). For example, taking homopolyethylene as an example, such a polymer can be produced by free radical polymerization, for example, in a high-pressure process, and is typically known as a highly branched ethylene homopolymer, commonly known as LDPE (low-density polyethylene), with a density of less than 0.945 g / cm 3 , usually 0.935g / cm 3 Below, for example, 0.900, 0.905, or 0.910 g / cm 3 to 0.920, 0.925, 0.927, 0.930, 0.935 or 0.945 g / cm 3 Unless otherwise specified, all polymer density values in this specification are determined according to ASTM D1505. Samples were molded according to ASTM D4703-10a, Procedure C, and allowed to stand for 40 hours under ASTM D618-08 (23±2°C and 50±10% relative humidity) before testing.

[0293] In another example, ethylene monomer can be polymerized by known gas, slurry and / or solution phase polymerization (e.g., using catalysts such as chromium-based catalysts, or single-site catalysts such as Ziegler-Natta and / or metallocene catalysts), which are well known in the polymerization art and will not be discussed further in this specification. In the case of making a more linear ethylene homopolymer (e.g., using gas or slurry phase polymerization with any of the above catalysts), it is referred to as HDPE (high density polyethylene), typically having a carbon density of 0.945 to 0.970 g / cm 3 In the range of 0.945g / cm 3 Density above.

[0294] 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 referred to herein include copolymers of ethylene and one or more C3-C20 α-olefin comonomers, such as C4-C12 α-olefin comonomers (preferably 1-butene, 1-hexene, 1-octene, or a mixture of two or more thereof in various embodiments). Ethylene copolymers (e.g., copolymers of ethylene and one or more C3 to C20 α-olefins) may contain at least 90, 94, 95, or 96 wt% (e.g., a range of 80, 85, 90, 80, 85, 93, 93, 95, 96, or 97 wt% to a range of 94, 95, 95.5, 91, 92, 97, 94, 97.5, or 98 wt%, at least 96 wt% or 96.5 wt%) of ethylene-derived units, based on the total amount of ethylene-derived units and comonomer-derived units, and may include any of the above lower values to any of the above higher values. For example, based on the total amount of ethylene-derived units and comonomer-derived units, the ethylene copolymer may contain 94 or 95 mass% to 97 or 98 mass% of ethylene-derived units. The balance of the copolymer (based on the ethylene-derived units and the comonomer-derived units) is made up 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 in an amount as low as 2, 2.5, 3, 3.5, 4, 4.5, 5, or 6 mass %, up to an amount as high as 3, 4, 5, 6, 7, 8, 9, 10, 15, or 20 mass %, ranging from the aforementioned low values to the aforementioned high values (where the high values are greater than the low values).

[0295] Regarding copolymers of ethylene, propylene, or other α-olefins, suitable comonomers are known, but in various embodiments, other α-olefin comonomers are also suitable. For example, the α-olefin comonomer can be linear or branched, and two or more comonomers can be used as needed. Examples of suitable comonomers include linear C3-C20 α-olefins (such as butene, hexene, octene, etc. as described above) and α-olefins having one or more C1-C3 alkyl branches or aromatic groups. For example, the comonomers include 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 illustrative only and is not intended to be limiting. In some embodiments, the comonomers include propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, and styrene.

[0296] In certain embodiments, the polymer may comprise an ethylene copolymer, or (as described above) may be an ethylene copolymer. Ethylene copolymers may be produced in gas, slurry or solution phase polymerizations, with some particularly preferred ethylene copolymers being produced in gas or slurry phase polymerizations. Specific examples are linear low density polyethylene (LLDPE), copolymers 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 LLDPE may have a viscosity ranging from 0.900, 0.905, 0.907, 0.910 g / cm 3 Low concentrations to 0.920, 0.925, 0.930, 0.935, 0.940 or 0.945 g / cm 3The density of LLDPE can be in the range of high concentrations. The density of LLDPE can be in the range of 0.902 to 0.945, can be in the range of 0.906 to 0.932, can be in the range of 0.908 to 0.926. LLDPE can be distinguished from the above-mentioned LDPE in several aspects, many of which are well known in the art, including the degree of branching in the produced polymer (which is often almost non-existent, if any), noting that LLDPE has substantially fewer long chain branches. In certain embodiments, the polymer of the polymer composition is or comprises a metallocene catalyst LLDPE (mLLDPE). In other embodiments, the polymer of the polymer composition is or comprises a Ziegler-Natta catalyst LLDPE (or ZN-LLDPE).

[0297] Additionally, in some embodiments, the polymer has a density of 0.905 to 0.945 g / cm 3 in the range of, for example, 0.905, 0.907, 0.908, 0.910, 0.911, 0.912, 0.913, 0.914 or 0.915 g / cm 3 Any lower value to 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 The range is from the above low value to the high value (e.g., 0.910 to 0.925 or 0.935 g / cm 3 , for example, 0.912 to 0.925 or 0.915 to 0.918 g / cm 3 ). In other embodiments, the polymer may have a viscosity of 0.945 g / cm 3 to 0.970g / cm 3 Density within the range of, higher density (such as HDPE).

[0298] In addition, the rheological properties of the polymer can affect the composition of the processing aid used to form the molded article. Generally, PPA compositions are preferably used in polymers having a melt index (MI or I2 measured according to ASTM D1238 at 190°C under a load of 2.16 kg) ranging from 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, and preferably less than 1.5 g / 2.0 min, and preferably less than 2.5 g / 3.0 min. Melt index ratio (MIR) (MIR is the ratio of the high load melt index to the melt index (HLMI) (measured according to ASTM D1238 at 190° C. and a load of 21.6 kg, or is defined as HLMI / MI) in this specification) in some embodiments of the polymer, generally having an MIR in the range of 10, 12 or 15 to 19, 20, 21, 22, 25, 27, 30, 35, 40, 45, 50, 60, 65, 70, 75, 80, 85, 90, 95 or 100. If desired, the MI in such a polymer can be less than 1.5 g / 10 min, such as less than 1.0 g / 10 min (e.g., 0.1, 0.2 or 0.5 g / 10 min to any one of 1.0 or 1.1, 1.2, 1.3, 1.4 or less than 1.5 g / 10 min).

[0299] The LLDPE is preferably at least one selected from the group consisting of Ziegler-Natta catalyst-based LLDPE and metallocene catalyst-based LLDPE, with metallocene catalyst-based LLDPE being particularly preferred.

[0300] The thermoplastic resin (A) may or may not be crystalline. When the thermoplastic resin (A) is crystalline, it preferably has a melting point of 80 to 300°C, more preferably 100 to 200°C. The non-crystalline thermoplastic resin (A) preferably has a processing temperature substantially equivalent to that of the crystalline thermoplastic resin (A) having a melting point range.

[0301] In the masterbatch disclosed herein, the mass ratio of the thermoplastic resin (A) to the processing aid (thermoplastic resin (A):processing aid) is preferably 99:1 to 1:99. This mass ratio is more preferably 97:3 to 50:50, even more preferably 95:5 to 60:40, and particularly preferably 92:8 to 70:30. This 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.

[0302] In the masterbatch of the present disclosure, the total content of the thermoplastic resin (A) and the processing aid is preferably 80% by mass or more, more preferably 90% by mass or more, further preferably 95% by mass or more, and particularly preferably 100% by mass.

[0303] The melt flow rate (MFR) of the masterbatch disclosed herein is preferably 0.01 g / 10 min or more, more preferably 0.1 g / 10 min or more, and even more preferably 1.0 g / 10 min or more. Furthermore, it is preferably 100 g / 10 min or less, more preferably 50 g / 10 min or less, and even more preferably 20 g / 10 min or less. Within this range, the processability is further improved.

[0304] In this specification, MFR is measured in accordance with ASTM D 1238 under the conditions of 190°C and a load of 2.16 kgf.

[0305] The masterbatch of the present disclosure may contain components other than the thermoplastic resin (A) and the processing aid.

[0306] The masterbatch disclosed herein can be obtained, for example, by performing a mixing step in which the processing aid disclosed herein is prepared in advance and added to the thermoplastic resin (A) and a mixer, etc., followed by a discharging step in which the mixture is discharged from the mixer, etc. Alternatively, the masterbatch can be obtained by performing a mixing step in which the thermoplastic resin (A) and the biodegradable polymer are added to a mixer, etc., followed by a discharging step in which the mixture is discharged from the mixer, etc. The present disclosure also relates to a method for producing the masterbatch described above, comprising the mixing step and the discharging step.

[0307] In the method for producing the masterbatch of the present disclosure, a molding step of molding the discharged product using a molding machine or the like may be performed after the discharging step.

[0308] The mixing step, discharge step, and molding step in the method for producing the masterbatch disclosed herein are the same as those described in the method for producing the processing aid disclosed herein. The shape of the masterbatch disclosed herein is not particularly limited and may be powder, granules, pellets, etc., but pellets are preferred due to their excellent handleability and ease of molding.

[0309] The masterbatch disclosed herein is particularly useful as a masterbatch for improving the processability of thermoplastic resins (particularly polyolefin resins).

[0310] <Thermoplastic Resin Composition>

[0311] The thermoplastic resin composition of the present disclosure comprises the processing aid and / or the masterbatch of the present disclosure and a thermoplastic resin (B), thereby achieving good processability (particularly extrusion processability).

[0312] As the thermoplastic resin (B), the same resin as the thermoplastic resin (A) can be used, and preferred aspects are also the same.

[0313] 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. However, from the viewpoint of obtaining better processability, it preferably contains the masterbatch of the present disclosure.

[0314] When the thermoplastic resin composition of the present disclosure includes the masterbatch of the present disclosure, the thermoplastic resin (A) and the thermoplastic resin (B) may be of the same type or different types.

[0315] In the thermoplastic resin composition disclosed herein, 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, still more preferably 0.10% by mass or more, and particularly preferably 0.15% by mass or more. Furthermore, it is preferably 5.0% by mass or less, more preferably 3.0% by mass or less, even more preferably 2.0% by mass or less, and 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, or 0.5% by mass or more, and may be 5% by mass or less, 2% by mass or less, 1.5% by mass or less, or 1.0% by mass or less.

[0316] The thermoplastic resin composition of the present disclosure may contain components other than the processing aid, the masterbatch, and the thermoplastic resin (B).

[0317] As components other than the above-mentioned processing aid, the above-mentioned masterbatch and the above-mentioned thermoplastic resin (B), for example, anti-fixing 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 enhancers such as rubber; antioxidants such as hindered phenol-based and phosphorus-based antioxidants; nucleating agents such as metal salts and acetal of sorbitol, anti-blocking agents, and the above-mentioned lubricant (A) can be used.

[0318] The thermoplastic resin composition disclosed herein can be obtained, for example, by performing a mixing step in which a masterbatch disclosed herein is prepared in advance and introduced into a mixer or the like to mix the thermoplastic resin (B) and the thermoplastic resin (B), followed by a discharge step in which the mixture is discharged from the mixer or the like. Alternatively, the thermoplastic resin (B), the biodegradable polymer, and, if necessary, the thermoplastic resin (A) can be introduced into a mixer or the like to mix the thermoplastic resin (B), followed by a discharge step in which the mixture is discharged from the mixer or the like. The present disclosure also relates to a method for producing the thermoplastic resin composition, comprising the mixing and discharge steps.

[0319] The method for producing the thermoplastic resin composition of the present disclosure may include a molding step of molding the discharged product using a molding machine or the like after the discharging step.

[0320] The mixing step, the discharging step, and the molding step in the method for producing the thermoplastic resin composition of the present disclosure are the same as those described in the method for producing the processing aid of the present disclosure.

[0321] <Molding>

[0322] The molded article of the present disclosure can be obtained by using the thermoplastic resin composition of the present disclosure and, for example, performing a molding step of molding the thermoplastic resin composition of the present disclosure.

[0323] The present disclosure also relates to a method for producing the molded article of the present disclosure, including a molding step.

[0324] It should be noted that the thermoplastic resin composition of the present disclosure is suitable for tube-shaped, film-shaped, or sheet-shaped molded articles, and can also be applied to molded articles of other shapes.

[0325] The molding step is the same as that described in the method for producing the processing aid of the present disclosure.

[0326] In the molding step, the molding temperature (extrusion temperature) is generally set at a temperature not lower than the melting point of the thermoplastic resin (B) and not higher than the decomposition temperature of the biodegradable polymer. In order to significantly exert the effect of the processing aid, the temperature is preferably set in the range of 160°C to 270°C.

[0327] In the case of extrusion molding, the above-mentioned molding temperature may be referred to as extrusion temperature.

[0328] The applications of the molded article of the present disclosure are not particularly limited, and examples thereof include bags, covering materials, tableware such as beverage containers, electric wires, cables, tubes, fibers, bottles, gasoline tanks, and other various industrial molded articles.

[0329] <Film>

[0330] The film of the present disclosure can be obtained by using the thermoplastic resin composition of the present disclosure, for example, by performing a molding step of molding the thermoplastic resin composition of the present disclosure.

[0331] The present disclosure also relates to a method for producing the molded article of the present disclosure, including a molding step.

[0332] It should be noted that the thermoplastic resin composition of the present disclosure is suitable for tube-shaped, film-shaped, or sheet-shaped molded articles, and can also be applied to molded articles of other shapes.

[0333] The molding step is the same as that described in the method for producing the processing aid of the present disclosure.

[0334] In the molding step, the molding temperature (extrusion temperature) is generally set at a temperature not lower than the melting point of the thermoplastic resin (B) and not higher than the decomposition temperature of the biodegradable polymer. In order to significantly exert the effect of the processing aid, the temperature is preferably set in the range of 160°C to 270°C.

[0335] In the case of extrusion molding, the above-mentioned molding temperature may be referred to as extrusion temperature.

[0336] The applications of the film of the present disclosure are not particularly limited, and examples thereof include bags, covering materials, tableware such as beverage containers, electric wires, cables, tubes, fibers, bottles, gasoline tanks, and various other industrial molded products.

[0337] While the embodiments have been described above, it should be understood that various changes in form and details may be made without departing from the spirit and scope of the claims.

[0338] Example

[0339] Next, the present disclosure will be described with reference to examples, but the present disclosure is not limited to these examples.

[0340] In Examples and Comparative Examples, the following materials were used.

[0341] (Additive (biodegradable polymer))

[0342] PBS-1: Polybutylene succinate (MFR: 22 g / 10 min, melting point: 114°C)

[0343] PBS-2: Polybutylene succinate (MFR: 4 g / 10 min, melting point: 85°C)

[0344] PBS-3: Polybutylene succinate (MFR: 250 g / 10 min, melting point: 114°C)

[0345] PLA-1: Polylactic acid (MFR: 3g / 10min, melting point: 153°C)

[0346] PLA-2: Polylactic acid (MFR: 30 g / 10 min, melting point: 172°C)

[0347] PLA-3: Polylactic acid (MFR: 110 g / 10 min, melting point: 174°C)

[0348] PBAT: Polybutylene terephthalate-adipate (MFR: 4g / 10min, melting point: 115°C)

[0349] (Additives (Synergizers))

[0350] PCL: polycaprolactone (Mw: 80,000, melting point: 55°C)

[0351] PEG-1: polyethylene glycol (Mn: 8,000, melting point: 63°C)

[0352] PEG-2: polyethylene glycol (Mn: 35,000, melting point: 63°C)

[0353] PEO-1: Polyethylene oxide (Mv: 150,000-400,000, melting point: 64°C)

[0354] PEO-2: Polyethylene oxide (Mv: 400,000-600,000, melting point: 65°C)

[0355] PEO-3: Polyethylene oxide (Mv: 600,000-1,100,000, melting point: 66°C)

[0356] MB50-002: Silicone (including ultra-high molecular weight silicone masterbatch, manufactured by Dupont)

[0357] GENIOPLAST PELLET S: Silicone (ultra-high molecular weight silicone, manufactured by Asahi Kasei Wakker)

[0358] Pebax MV1072: Polyamide-polyether block copolymer (made by Arkema)

[0359] (Additive (ethylene-vinyl alcohol copolymer))

[0360] EVOH-1: Ethylene-vinyl alcohol copolymer (ethylene content: 38 mol%, MFR: 1.5 g / 10 min)

[0361] EVOH-2: Ethylene-vinyl alcohol copolymer (ethylene content: 32 mol%, MFR: 1.6 g / 10 min)

[0362] EVOH-3: Ethylene-vinyl alcohol copolymer (ethylene content: 44 mol%, MFR: 1.6 g / 10 min)

[0363] EVOH-4: Ethylene-vinyl alcohol copolymer (ethylene content: 38 mol%, MFR: 50 g / 10 min)

[0364] (Additive (lubricant (A)))

[0365] Polysorbate60: Polysorbate 60

[0366] Zn-St: Zinc stearate (Zinc stearate)

[0367] Mg-C18(OH):Magnesium 12-hydroxystearate

[0368] (Additives (Anti-degradation agents))

[0369] Phenol: Pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]

[0370] Phosphoric acid series: tris(2,4-di-tert-butylphenyl) phosphite

[0371] (Base resin, carrier resin)

[0372] LLDPE-1: Metallocene-catalyzed linear low-density polyethylene (MFR: 0.7 g / 10 min, melting point: 123°C, d = 0.926, MIR = 28.1)

[0373] LLDPE-2: Metallocene-catalyzed linear low-density polyethylene (MFR: 2.0 g / 10 min, melting point: 121°C, d = 0.925, MIR = 23.6)

[0374] LLDPE-3: Ziegler-Natta catalyzed linear low-density polyethylene (MFR: 0.8 g / 10 min, melting point: 123°C, d = 0.925, MIR = 27.0)

[0375] LLDPE-4: Ziegler-Natta catalyzed linear low-density polyethylene (MFR: 2.0 g / 10 min, melting point: 121°C, d = 0.918, MIR = 23.2)

[0376] LDPE: Low-density polyethylene (MFR: 2.0 g / 10 min, melting point: 111°C, d = 0.924)

[0377] MFR:

[0378] The MFR (g / 10 min) of the additives, base resin, and carrier resin was measured in accordance with ASTM D 1238 at 190° C. and a load of 2.16 kgf.

[0379] MIR:

[0380] The MIR of the matrix resin and the carrier resin is calculated by HLMI / MI.

[0381] HLMI: MFR (g / 10min) at 190°C and a load of 21.6 kgf according to ASTM D 1238

[0382] MI: MFR (g / 10min) at 190°C and a load of 2.16 kgf according to ASTM D 1238

[0383] Melting point:

[0384] A DSC apparatus (manufactured by SEIKO) was used, and the temperature corresponding to the maximum value in the heat of fusion curve when the temperature was increased at a rate of 10°C / min was defined as the melting point.

[0385] Examples A1 to A15, Comparative Examples A1 to A10

[0386] Each material was dry-blended with a matrix resin (LLDPE-1) in the ratios shown in Table 1 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 1.

[0387] It should be noted that in Comparative Examples A3 to A10, extrusion was not possible due to slippage.

[0388] Examples B1 to B8, Comparative Examples B1 to B6

[0389] First, additives were dry-blended in the proportions shown in Table 2 to obtain a processing aid. Next, the resulting processing aid was dry-blended with a base resin (LLDPE-1) in the proportions shown in Table 2 to obtain a thermoplastic resin composition. The processability of the resulting thermoplastic resin composition was evaluated using the extrusion test described below. The results are shown in Table 2.

[0390] It should be noted that, in Comparative Examples B3 to B6, extrusion was not possible due to slippage.

[0391] Examples C1 to C15, Comparative Examples C1 to C10, Examples D1 to D9, Comparative Examples D1 to D11

[0392] First, the carrier resin and additives were melt-kneaded in the proportions shown in Tables 3 and 4 using a twin-screw extruder (TEXαIII, manufactured by The Japan Steel Works, Ltd.) at a barrel temperature of 180-200°C, a die temperature of 200°C, and a screw speed of 400 rpm to produce a masterbatch (MB). Next, the resulting masterbatch was dry-blended with a matrix resin (LLDPE-1) in the proportions shown in Tables 3 and 4 to produce a thermoplastic resin composition. The processability of the resulting thermoplastic resin composition was evaluated using the extrusion test described below. The results are shown in Tables 3 and 4.

[0393] Examples E1 to E13, Comparative Example E1

[0394] First, additives were dry-blended in the proportions shown in Table 5 to obtain a processing aid. Next, the resulting processing aid was dry-blended with a base resin (LLDPE-1) in the proportions shown in Table 5 to obtain a thermoplastic resin composition. The processability of the resulting thermoplastic resin composition was evaluated using the extrusion test described below. The results are shown in Table 5.

[0395] Examples F1 to F16, Comparative Example F1

[0396] First, the carrier resin and additives were melt-kneaded in the proportions shown in Table 6 using a twin-screw extruder (TEXαIII, manufactured by The Japan Steel Works, Ltd.) at a barrel temperature of 180-200°C, a die temperature of 200°C, and a screw speed of 400 rpm to produce a masterbatch (MB). This masterbatch was then dry-blended with a matrix resin (LLDPE-1) in the proportions shown in Table 6 to produce a thermoplastic resin composition. The processability of the resulting thermoplastic resin composition was evaluated using the extrusion test described below. The results are shown in Table 6.

[0397] It should be noted that in Tables 1 to 4, the following contents are the same.

[0398] Examples A3, B7

[0399] Examples A10, B8

[0400] Examples C3, D8

[0401] Examples C10, D9

[0402] Comparative Examples A1, B1, C1, E1, F1

[0403] Comparative Examples A2 and B2

[0404] <Extrusion Evaluation>

[0405] Each material was extruded using a single-screw extruder (Rheomex OS, L / D: 33, screw diameter: 20 mm, die diameter: 2 mm, manufactured by HAAKE) at a barrel temperature of 170-200°C, a die temperature of 200°C, and a shear rate of 450 / s for 60 minutes, and evaluated using the following parameters.

[0406] Before each test run, a linear low-density polyethylene (LLDPE) supplemented with 15% by mass silica was added to the hopper, the screw speed was increased to 150 rpm, and a purge was performed for approximately 15 minutes. Next, the same LLDPE-1 used in the test was added and purge was performed for approximately 15 minutes. The screw speed was then returned to 30 rpm and extrusion was continued until the temperature stabilized. After confirming that the initial pressure had recovered, the next test was performed. If the initial pressure did not recover, the purge was repeated until the initial pressure returned, and the next test was performed.

[0407] (Melt Fracture (MF) State)

[0408] Extrusion of the matrix resin alone was continued until the pressure stabilized with melt fracture occurring throughout the entire extrusion process. The time at which the screw was subsequently observed was set to 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 time zero. The appearance of the strands at the beginning of extrusion and at the end of extrusion was visually inspected and palpated. Changes in MF observed during the initial extrusion phase were evaluated according to the following criteria. Smaller values are preferred.

[0409] 1: MF disappears completely

[0410] 2: MF is reduced but not completely eliminated

[0411] 3: MF has no change or has hardly decreased compared to the case of base resin only

[0412] (Pressure stability)

[0413] After the start of extrusion, measure the extrusion pressure for 50 to 60 minutes and calculate its standard deviation. The closer the value to 0, the better.

[0414] (Die Head Buildup (DBU))

[0415] The state of the die after extrusion was visually checked, and the presence of DBU (die drool) was evaluated.

[0416] In Tables 1 to 4, the evaluation was conducted in three stages according to the following criteria: The smaller the value, the better.

[0417] 1: No DBU occurs

[0418] 2: DBU occurs in small amounts

[0419] 3: DBU occurs in large numbers

[0420] In Tables 5 and 6, the evaluation was performed on a five-step scale of 1 to 5. The smaller the value, the less DBU was generated, which is better, and 1 means no DBU was generated.

[0421] In addition, Tables 1 to 4 include both three-stage evaluation and five-stage evaluation.

[0422] (Melt fracture (MF) disappearance time)

[0423] The time from time zero described above for the MF state to when the MF disappears is measured. The shorter the time, the better. If the MF does not disappear after 60 minutes of extrusion, it is recorded as "-".

[0424]

[0425]

[0426]

[0427]

[0428]

[0429]

[0430] Examples 1 to 83, Comparative Examples 1 to 3

[0431] First, the carrier resin and the additives were melt-kneaded in a twin-screw extruder (TEX25αIII manufactured by Nippon Steel Works) at a barrel temperature of 180 to 200°C, a die temperature of 200°C, and a screw speed of 400 rpm in a manner such that the concentration of the additives was 25% by mass, to obtain a masterbatch (MB). Next, the processability of the obtained masterbatch when dry-blended with the matrix resin in the proportions shown in Tables 7 to 9 was evaluated according to the following extrusion evaluation. The results are shown in Tables 7 to 9. It should be noted that the materials of the additives used do not contain fluorine, and therefore the fluorine content in the processing aid is 0% by mass.

[0432] <Extrusion Evaluation>

[0433] For Examples 1 to 72 and Comparative Examples 1 to 3, each material was extruded using a single-screw extruder (manufactured by HAAKE, Rheomex OS, L / D: 33, screw diameter: 20 mm, die diameter: 2 mm) at a barrel temperature of 170 to 200°C, a die temperature of 200°C, and a shear rate of 450 / s for 60 minutes, and evaluated using the following items.

[0434] Prior to each test run, linear low-density polyethylene (LLDPE) supplemented with 15% by mass silica was added to the feed hopper, the screw speed was increased to 150 rpm, and a purge was performed for approximately 15 minutes. Next, the same base resin used in the test was added and purge was performed for approximately 15 minutes. The screw speed was then returned to 30 rpm and extrusion was continued until the temperature stabilized. After confirming the initial pressure had recovered, the next test was performed. If the initial pressure did not recover, the purge was repeated until the initial pressure had returned before the next test.

[0435] (Melt Fracture (MF) State)

[0436] Extrusion of the matrix resin alone was continued until the pressure stabilized with melt fracture occurring throughout the entire extrusion process. The time at which the screw was subsequently observed was set to 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 time zero. The appearance of the strands at the beginning of extrusion and at the end of extrusion was visually inspected and palpated. Changes in MF observed during the initial extrusion phase were evaluated according to the following criteria. Smaller values are preferred.

[0437] Vanish: MF completely disappears

[0438] Does not disappear: MF does not change compared to the case of only the matrix resin, or MF decreases but does not disappear at all

[0439] (Die Head Buildup (DBU))

[0440] For samples in which MF completely disappeared, extrusion evaluation was performed under long-term molding (3 hours), and the state of the die after extrusion was visually confirmed to evaluate the presence of DBU (die drool).

[0441] The evaluation was performed on a scale of 1 to 5. The smaller the value, the less DBU was generated, and the better. 1 means no DBU was generated.

[0442] (Storage stability test)

[0443] For Examples 29, 36, 41, 46, and 47, strand samples were collected after long-term molding (3 hours) and allowed to stand at 80°C for 24 hours. After 24 hours, the strand surface slip properties were evaluated by sensory evaluation (tactile feel). The slip properties before and after the test were evaluated using the following criteria. The results are shown in Table 8.

[0444] Yes: The sliding property after the test is higher than before the test

[0445] None: No change before and after the test

[0446] <Film Forming>

[0447] For Examples 73 to 83, a single-layer inflation molding machine (inflation die diameter 25 mm, die gap 0.8 mm) was used to extrude each material for 70 minutes at a barrel temperature of 170°C, a die temperature of 200°C, and a shear rate of 90 / second, and the evaluation was performed using the following items. It should be noted that before each test run, a linear low-density polyethylene to which 15% by mass of silica was added was put into the feed hopper and purged for about 60 minutes. Next, the same base resin as used in the test was put in and purged for about 60 minutes. After confirming that the initial pressure had recovered, the next experiment was performed. If the initial pressure had not recovered, the above-mentioned purging operation was repeated until the initial pressure was restored before the next experiment was performed.

[0448] (Melt fracture (MF) disappearance time)

[0449] Extrusion of the base resin alone was continued until the pressure stabilized with melt fracture occurring throughout the body. The moment the screw was subsequently observed was set to zero, and extrusion was continued for 70 minutes. For samples using processing aids or masterbatches, these were added to the feed hopper at time zero. The appearance of the film at the beginning of extrusion and after the start of extrusion was visually and palpated, and the time it took for the film to disappear was recorded. The shorter the time, the better. The results are shown in Table 9.

[0450] (Pressure stability)

[0451] After MF disappears and 5 minutes have passed, the extrusion pressure is measured at 1-minute intervals for 20 minutes, and the standard deviation is calculated. The closer the value is to 0, the better. The results are shown in Table 9.

[0452] (film thickness)

[0453] Film samples were collected for 3 minutes at 50, 60, and 70 minutes after the start of film extrusion. The sampled film was measured at a single measurement location in the TD direction of the film. The film thickness was measured at 25 locations (75 locations in total) in the MD direction at 25°C. The average, maximum, and minimum values were calculated. Thickness nonuniformity was also calculated using the following formula. The results are shown in Table 9.

[0454] Thickness variation (%) = (maximum thickness (maximum value) - minimum thickness (minimum value)) / average thickness (average value) × 100

[0455] <MFR of Masterbatch>

[0456] For Examples 84 to 91, the carrier resin and additives were melt-kneaded in the proportions shown in Table 10 using a twin-screw extruder (TEX25αIII manufactured by The Japan Steel Works, Ltd.) at a barrel temperature of 180-200°C, a die temperature of 200°C, and a screw speed of 400 rpm to achieve an additive concentration of 25% by mass to obtain a masterbatch (MB). The MFR (g / 10 min) of the resulting masterbatch was measured (according to ASTM D 1238 at 190°C and a load of 2.16 kgf). The results are shown in Table 10.

[0457]

[0458] [Table 8]

[0459]

[0460] ※2: ((Additive 1 + Additive 2 + Additive 3) / (Base resin + Carrier resin + Additive 1 + Additive 2 + Additive 3)

[0461]

[0462]

Claims

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

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

3. The processing aid according to claim 1 or 2, wherein The biodegradable polymer is an aliphatic polyester.

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. The processing aid according to any one of claims 1 to 4, wherein The biodegradable polymer has a melt flow rate of 0.01 g / 10 min to 500 g / 10 min at 190° C. and a load of 2.16 kgf.

6. The processing aid according to any one of claims 1 to 5, wherein The processing aid comprises a synergist, and the synergist is at least one selected from the group consisting of polyols having a melting point of 80° C. or less, polycaprolactone, silicone, 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 any one of claims 6 to 8, wherein The mass ratio of the biodegradable polymer to the synergist (biodegradable polymer: synergist) is 99.9:0.1 to 10:

90.

10. The processing aid according to any one of claims 1 to 9, wherein The processing aid comprises 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 minutes or less at 190° C. and a load of 2.16 kgf.

12. The processing aid according to claim 10 or 11, wherein The ethylene content of the ethylene-vinyl alcohol copolymer is 10 mol% to 50 mol%.

13. The processing aid according to any one of claims 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.

14. The processing aid according to any one of claims 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.

15. The processing aid according to any one of claims 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 1-98:1-98:1-98.

16. The processing aid according to any one of claims 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 25-90:5-70:5-70.

17. The processing aid according to any one of claims 1 to 16, wherein The processing aid includes a lubricant (A), and the lubricant (A) 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 or 18, 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 any one of claims 17 to 19, 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 any one of claims 17 to 20, 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. The processing aid according to any one of claims 1 to 21, wherein The processing aid is substantially fluorine-free. 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. The masterbatch according to claim 24, wherein The polyolefin resin is polyethylene.

26. The masterbatch according to any one of claims 23 to 25, 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 any one of claims 23 to 26, wherein The masterbatch has a melt flow rate of 0.01 g / 10 min 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 any one of claims 1 to 22 and / or the masterbatch according to any one of claims 23 to 27, and a thermoplastic resin (B).

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

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

31. The thermoplastic resin composition according to any one of claims 28 to 30, wherein The content of the processing aid is 0.001% by mass to 5% by mass.

32. A film using the thermoplastic resin composition according to any one of claims 28 to 31.

33. The method for producing a processing aid according to any one of claims 1 to 22, comprising a mixing step and a discharging step.

34. The method for producing a masterbatch according to any one of claims 23 to 27, comprising a mixing step and a discharging step.

35. A method for producing a thermoplastic resin composition according to any one of claims 28 to 31, comprising a mixing step and a discharging step.

36. The method for producing a film according to claim 32, comprising a forming step.

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