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

Abstract

To provide a processing aid and a master batch which can improve processibility of a thermoplastic resin, a thermoplastic resin composition and a molded body using them, and a method for manufacturing them.SOLUTION: A processing aid contains a lubricant (A) and a resin (B), wherein the resin (B) includes a structural unit represented by formula 1: -X-(CR1R2)n-Y-(CR3R4)m-Z-.SELECTED DRAWING: None

Description

Technical Field

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

Background Art

[0002] In the processing of melt-processable thermoplastic resins, it is necessary to extrude at a high speed in order to improve productivity and reduce costs. However, there is always a critical shear rate in melt-processable thermoplastic resin compositions, and when this rate is exceeded, a state called melt fracture occurs in which the surface becomes rough, and a good molded product cannot be obtained.

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

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0005] An object of the present disclosure is to provide a processing aid and a masterbatch that can improve the processability of thermoplastic resins, and a thermoplastic resin composition and a molded article using them. Another object of the present disclosure is to provide methods for producing them.

Means for Solving the Problems

[0006] The present disclosure (1) comprises a lubricant (A) and a resin (B), The resin (B) is a processing aid containing a structural unit represented by the following formula 1. -X-(CR 1 R 2 ) n -Y-(CR 3 R 4 ) m -Z- (Formula 1) (In formula 1, X represents a single bond or a divalent group which may have a functional group, Y and Z each independently represent a group consisting of at least one selected from the group consisting of a single bond, -O-, -C(=O)-, -C(=O)O-, -OC(=O)O-, -C(=NR')-, -C(=NR')O-, -OC(=NR')O-, -S-, -S(=O)-, -S(=O)O-, -OS(=O)O-, -S(=O)2-, -S(=O)2O-, -OS(=O)2O-, -P(=O)-, -P(=O)O-, -OP(=O)O-, -P(=O)2-, -P(=O)2O-, -OP(=O)2O-, -NR'-, and -C(OR')R'- (wherein R' is independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms in each occurrence); R 1 , R 2 , R 3 and R 4 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, n and m are each independently an integer of 0 to 10; At least one of X, Y, and Z is -C(=O)-, -C(=O)O-, -OC(=O)O-, or -C(OR')R'-.

[0007] The present disclosure (2) is the processing aid according to the present disclosure (1) which is substantially free of fluorine.

[0008] The present disclosure (3) is the processing aid according to the present disclosure (1) or (2), in which the lubricant (A) is at least one selected from the group consisting of waxes, alcohols, and surfactants.

[0009] The present disclosure (4) is the processing aid according to any one of the present disclosures (1) to (3), wherein the lubricant (A) is at least one selected from the group consisting of a sugar-based surfactant, a metal soap, and a polyethylene wax.

[0010] In the present disclosure (5), in the formula 1, X is 1 and X 2 is a divalent group composed of at least one selected from the group consisting of, X 1 is a group composed of at least one selected from the group consisting of -C(=O)-, -C(=NR’)-, -S(=O)2-, -NR’-, -CR’R’-, and -C(OR’)R’- (wherein R’ is, in each occurrence, independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms). X 2 is the processing aid according to any one of the present disclosures (1) to (4), which is an aromatic hydrocarbon group having 1 to 12 carbon atoms that may have a substituent.

[0011] In the present disclosure (6), in the formula 1, X is a divalent group containing at least one selected from the group consisting of -C(=O)-, -CR’R’-, and -C(OR’)R’- (wherein R’ is, in each occurrence, independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms). It is the processing aid according to the present disclosure (5).

[0012] In the present disclosure (7), in the formula 1, Y and Z are each independently a single bond, -O-, -C(=O)-, -C(=O)O-, -C(=NR’)-, -C(=NR’)O-, -S-, -S(=O)2-, -S(=O)2O-, -NR’-, and -C(OR’)R’- (wherein R’ is, in each occurrence, independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms). It is the processing aid according to any one of the present disclosures (1) to (6).

[0013] The present disclosure (8) is the processing aid described in the present disclosure (7), wherein in Formula 1, Y and Z are each independently a group composed of at least one selected from the group consisting of a single bond, -O-, -C(=O)-, and -C(=O)O-.

[0014] The present disclosure (9) is the processing aid according to any one of the present disclosures (1) to (8), wherein the melting point of the resin (B) is 65°C or higher.

[0015] The present disclosure (10) is the processing aid according to any one of the present disclosures (1) to (9), wherein the resin (B) is at least one selected from the group consisting of polylactic acid, polybutylene succinate, ethylene-vinyl alcohol copolymer, and polybutylene succinate adipate.

[0016] The present disclosure (11) is the processing aid according to any one of the present disclosures (1) to (10), wherein the lubricant (A) is at least one selected from the group consisting of polysorbate, zinc stearate, magnesium 12-hydroxystearate, and polyethylene wax, and the resin (B) is at least one selected from the group consisting of polylactic acid, polybutylene succinate, and ethylene-vinyl alcohol copolymer.

[0017] The present disclosure (12) is a masterbatch containing the processing aid according to any one of the present disclosures (1) to (11) and a thermoplastic resin (C).

[0018] The present disclosure (13) is the masterbatch according to the present disclosure (12), wherein the thermoplastic resin (C) is a polyolefin resin.

[0019] The present disclosure (14) is the masterbatch according to the present disclosure (12) or (13), wherein the thermoplastic resin (C) is at least one selected from the group consisting of metallocene-catalyzed linear low-density polyethylene and Ziegler-Natta-catalyzed linear low-density polyethylene, and the mass ratio of the thermoplastic resin (C) to the processing aid (thermoplastic resin (C):processing aid) is 92:8 to 70:30.

[0020] The present disclosure (15) is a thermoplastic resin composition comprising a processing aid described in any one of the present disclosures (1) to (11) and / or a masterbatch described in any one of the present disclosures (12) to (14), and a thermoplastic resin (D).

[0021] The present disclosure (16) is the thermoplastic resin composition described in the present disclosure (15), wherein the thermoplastic resin (D) is a polyolefin resin.

[0022] The present disclosure (17) is the thermoplastic resin composition described in the present disclosure (15) or (16), wherein the thermoplastic resin (D) is at least one selected from the group consisting of a metallocene-catalyzed linear low-density polyethylene and a Ziegler-Natta-catalyzed linear low-density polyethylene, and the content of the processing aid is 0.02 to 3% by mass.

[0023] The present disclosure (18) is a molded article using the thermoplastic resin composition described in any one of the present disclosures (15) to (17).

[0024] The present disclosure (19) is the molded article described in the present disclosure (18), which is in a tubular, film or sheet form.

[0025] The present disclosure (20) is a method for producing a processing aid described in any one of the present disclosures (1) to (11), which includes a mixing step and an extrusion step.

[0026] The present disclosure (21) is a method for producing a masterbatch described in any one of the present disclosures (12) to (14), which includes a mixing step and an extrusion step.

[0027] The present disclosure (22) is a method for producing a thermoplastic resin composition described in any one of the present disclosures (15) to (17), which includes a mixing step and an extrusion step.

[0028] The present disclosure (23) is a method for producing a molded article described in the present disclosure (18) or (19), which includes a molding step.

Advantages of the Invention

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

Embodiments for Carrying Out the Invention

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

[0031] <Processing Aid> The processing aid of the present disclosure includes a lubricant (A) and a resin (B), wherein the resin (B) contains a structural unit represented by the following formula 1. -X-(CR 1 R 2 ) n -Y-(CR 3 R 4 ) m -Z- (Formula 1) (In Formula 1, X is a divalent group which may have a single bond or a functional group, Y and Z are each independently a group composed of at least one selected from the group consisting of a single bond, -O-, -C(=O)-, -C(=O)O-, -OC(=O)O-, -C(=NR’)-, -C(=NR’)O-, -OC(=NR’)O-, -S-, -S(=O)-, -S(=O)O-, -OS(=O)O-, -S(=O)2-, -S(=O)2O-, -OS(=O)2O-, -P(=O)-, -P(=O)O-, -OP(=O)O-, -P(=O)2-, -P(=O)2O-, -OP(=O)2O-, -NR’-, and -C(OR’)R’- (wherein R’ is independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms at each occurrence).), R 1 、R 2 、R 3 and R 4 are each independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, n and m are each independently an integer from 0 to 10, at least one of X, Y and Z is -C(=O)-, -C(=O)O-, -OC(=O)O- or -C(OR’)R’-.

[0032] The above lubricant (A) is an additive that reduces friction and improves slipperiness, and examples thereof include waxes, alcohols, surfactants, and the like. These can be used alone, one selected from these, or two or more thereof can be used in combination. The above lubricant (A) is preferably at least one selected from the group consisting of waxes, alcohols, and surfactants, more preferably at least one selected from the group consisting of waxes and surfactants, and even more preferably a surfactant.

[0033] Examples of the above waxes include pure hydrocarbon-based ones such as liquid paraffin, natural paraffin, micro wax, synthetic paraffin, polyethylene wax, polyethylene / polypropylene wax, etc.; fatty acid-based ones such as higher fatty acids and oxy fatty acids; fatty acid amide-based ones such as fatty acid amide and bis fatty acid amide; fatty acid ester-based ones such as polyhydric alcohol esters of fatty acids such as lower alcohol esters of fatty acids, glycerides, polyglycol esters of fatty acids, and aliphatic alcohol esters of fatty acids (ester waxes). Among them, pure hydrocarbon-based waxes and fatty acid ester-based waxes are preferred, and pure hydrocarbon-based waxes are more preferred. As the pure hydrocarbon-based waxes, polyethylene wax and polyethylene / polypropylene wax are preferred, and polyethylene wax is more preferred. As the fatty acid ester-based waxes, adipic acid ester and glycerin fatty acid ester are preferred. Examples of the above polyethylene wax include generally polymerized polyethylene wax, metallocene catalyst type polyethylene wax, acid-modified type polyethylene wax, oxidized type (slightly oxidized, high acid value) polyethylene wax, aromatic monomer-modified polyethylene wax, etc. As the acid-modified type, those copolymerized with vinyl carboxylic acids such as acrylic acid and methacrylic acid, as the oxidized type, those obtained by air oxidizing or thermally decomposing polyethylene, and as the aromatic monomer-modified polyethylene wax, those obtained by graft polymerization modification of styrene monomer can be mentioned.

[0034] Examples of fatty acid ester waxes include phthalic acid esters, dimethyl and diethyl succinates and related esters, glycerol monoacetate, glycerol diacetate, glycerol triacetate, glycerol monoacid esters, citric acid esters, adipic acid esters, stearic acid esters, oleic acid esters, and the like. These may be used alone or in combination of two or more.

[0035] Examples of adipic acid esters include, for example, diesters of adipic acid. Specifically, dimethyl adipate, dibutyl adipate, bis[2-(2-methoxyethoxy)ethyl] adipate, bis(butyl diglycol) adipate, bis(methyl diglycol) adipate, benzyl[2-(2-methoxyethoxy)ethyl] adipate, di-n-butyl adipate, dioctyl adipate, methyl diglycol butyl diglycol adipate, benzyl methyl glycol adipate, benzyl butyl diglycol adipate, diisononyl phthalate, and the like. These may be used alone or in combination of two or more. Among them, diisononyl phthalate and dioctyl adipate are preferred.

[0036] Examples of the glycerin fatty acid esters include glycerin monostearate, glycerin monobehenate, glycerin mono-12-hydroxystearate, glycerin monooleate, glycerin monocaprylate, glycerin monocaprate, glycerin monolaurate, glycerin diacetomonolaurate, succinic acid fatty acid monoglyceride, citric acid fatty acid monoglyceride, diacetyl tartaric acid fatty acid monoglyceride, diglycerin laurate, diglycerin stearate, diglycerin oleate, diglycerin monolaurate, diglycerin monomyristate, diglycerin monostearate, diglycerin monooleate, tetraglycerin stearate, decaglycerin laurate, decaglycerin stearate, decaglycerin oleate, polyglycerin polyricinoleate, propylene glycol monolaurate, propylene glycol monopalmitate, propylene glycol monostearate, propylene glycol monooleate, propylene glycol monobehenate, and the like. These may be used alone or in combination of two or more. Among them, glycerin diacetomonolaurate and decaglycerin stearate are preferred.

[0037] The acid value of the above waxes is preferably 40 mgKOH / g or less, more preferably 30 mgKOH / g or less, still more preferably 20 mgKOH / g or less. The lower limit is not particularly limited and may be 0 mgKOH / g. Within the above range, the effect of improving processability is better. The acid value is the number of milligrams of potassium hydroxide required to neutralize the free acid contained in 1 g of the waxes. The acid value of the waxes can be measured, for example, by a general neutralization titration method (JIS K 0070:1992).

[0038] The melting point of the above waxes is preferably 40°C or higher, more preferably 60°C or higher, still more preferably 80°C or higher, and preferably 200°C or lower, more preferably 160°C or lower, still more preferably 130°C or lower. Within the above range, the effect of improving processability is better. In this specification, the melting point is the temperature corresponding to the maximum value in the heat of fusion curve when the temperature is raised at a rate of 10 °C / min using a differential scanning calorimetry (DSC) apparatus.

[0039] The melt viscosity of the above waxes at 140 °C is preferably 20 mPa·s or more, more preferably 40 mPa·s or more, still more preferably 60 mPa·s or more, and is preferably 500 mPa·s or less, more preferably 400 mPa·s or less, and even more preferably 350 mPa·s or less. If it is within the above range, the effect of improving processability will be better. The above melt viscosity is a value measured in accordance with ISO11443, using a flow tester (manufactured by Shimadzu Corporation) and a 2φ - 8L die, keeping a 2 g sample pre-heated at 140 °C for 5 minutes at the above temperature under a load of 0.7 MPa.

[0040] Examples of the above alcohols include fatty alcohol-based alcohols such as higher alcohols; polyhydric alcohol-based alcohols such as polyglycol and polyglycerol. These may be only one kind or two or more kinds.

[0041] Examples of the fatty alcohol include lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol, behenyl alcohol, etc. These may be only one kind or two or more kinds.

[0042] Examples of the surfactant include anionic surfactants such as metal soaps and ammonium salt-based surfactants; cationic surfactants such as alkylamine salts and quaternary ammonium salts; nonionic surfactants such as ester type, ether type, ester / ether type, and amide type surfactants; and amphoteric surfactants such as aminocarboxylates, alkylbetaines, and alkylimidazoline derivatives. Among them, anionic surfactants or nonionic surfactants are preferred. As the anionic surfactant, metal soaps are preferred, specifically, carboxylates, sulfates, sulfonates, and phosphate esters are preferred. As the nonionic surfactant, ester / ether type is preferred, specifically, sugar type surfactants are preferred.

[0043] Examples of the metal soap include fatty acid salts, polysulfonate salts, polycarboxylate salts, alkyl sulfate ester salts, alkylaryl sulfonate salts, alkylnaphthalene sulfonate salts, dialkyl sulfonate salts, dialkyl sulfosuccinate salts, alkyl phosphate salts, polyoxyethylene alkyl ether sulfate salts, polyoxyethylene alkylaryl ether sulfate salts, and polyoxyethylene alkyl phosphate sulfonate salts. Specifically, for example, sodium dodecylbenzenesulfonate, sodium lauryl sulfate, sodium polyoxyethylene lauryl ether sulfate, and polyoxyethylene nonylphenyl ether sulfate ester salt can be mentioned. These may be used alone or in combination of two or more.

[0044] The metal soap is preferably a compound represented by the following general formula (1), for example. (R 5 COO) n1 M 1 (1) (In the 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, and M 1is 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.)

[0045] In the general formula (1), when n1 is an integer of 2 or more, a plurality of R 5 may be the same as or different from each other.)

[0046] R 5 The alkyl group having 1 to 21 carbon atoms of may be a linear alkyl group, a branched alkyl group, or may contain an alicyclic structure.)

[0047] R 5 The alkyl group having 1 to 21 carbon atoms of corresponds to the carboxylic acid residue obtained by removing the carboxyl group (COOH) from the carboxylic acid having 1 to 22 carbon atoms represented by R 5 COOH. Examples of the carboxylic acid residue include acetic acid residue, propionic acid residue, butanoic acid residue, pentanoic acid residue, acrylic acid residue, methacrylic acid residue, octylic acid residue (2-ethylhexanoic acid residue), neodecanoic acid residue, naphthenic acid residue, isononanoic acid residue, eleostearic acid residue, tall oil fatty acid residue, coconut oil fatty acid residue, soybean oil fatty acid residue, linseed oil fatty acid residue, safflower oil fatty acid residue, dehydrated castor oil fatty acid residue, camellia oil fatty acid residue, lauric acid residue, myristic acid residue, palmitic acid residue, stearic acid residue, isostearic acid residue, oleic acid residue, 12-hydroxystearic acid residue, and the like.)

[0048] R 5 The alkyl group having 1 to 21 carbon atoms of 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, from the viewpoint of improving processability.)

[0049] M 1is 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.

[0050] n1 is a numerical value determined by the valence of the metal atom of M 1 and for example when M 1 is boron, n1 is 3, and when M 1 is cobalt, n1 is 2.

[0051] The above metal soaps also include the form of fatty acid metal borate salts. The fatty acid metal borate salts are, for example, compounds represented by the following general formula (2). (R 6 COO-M 2 -O)3B (2) (In the above general formula (2), R 6 is a hydrogen atom or an alkyl group having 1 to 21 carbon atoms, and M 2 is boron, magnesium, aluminum, calcium, manganese, iron, cobalt, nickel, tin, antimony, copper, zinc, molybdenum, vanadium, strontium, zirconium, barium, bismuth, lead, gold, or platinum.)

[0052] In the general formula (2), the alkyl group having 1 to 21 carbon atoms of R 6 is the same as the alkyl group having 1 to 21 carbon atoms of R 5 in the general formula (1). Similarly, in the general formula (2), the metal of M 2 is the same as the metal of M 1 in the general formula (1).

[0053] The above metal soaps may be used alone or two or more metal soaps having different structures may be used together.

[0054] Specific examples of the above metal soaps include metal salts of stearic acid, metal salts of hydroxystearic acid, and the like. The above 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. In addition, examples of the metal constituting the above metal salt include zinc, magnesium, calcium, and the like. It is preferably at least one selected from the group consisting of zinc, magnesium, and calcium, and more preferably at least one selected from the group consisting of zinc and magnesium. The above metal soap can be produced by a known method, and a commercially available product may be used.

[0055] Examples of the above ammonium salt-based anionic surfactant include fatty acid ammonium salts. For example, ammonium lauryl sulfate, ammonium polyoxyethylene lauryl ether sulfate, and the like can be mentioned. The anionic surfactant may be only one kind or two or more kinds.

[0056] Examples of the cationic surfactant include, for example, alkylamine salts and quaternary ammonium salts. Specifically, for example, stearylamine acetate, trimethyl coconut ammonium chloride, trimethyl tallow ammonium chloride, dimethyldioleyl ammonium chloride, methyl oleyl diethanol chloride, tetramethyl ammonium chloride, lauryl pyridinium chloride, lauryl pyridinium bromide, lauryl pyridinium disulfate, cetyl trimethyl ammonium chloride, cetyl pyridinium bromide, 4-alkyl mercaptopyridine, poly(vinyl pyridine)-dodecyl bromide, dodecyl benzyl triethyl ammonium chloride can be mentioned. The cationic surfactant may be only one kind or two or more kinds.

[0057] Examples of amphoteric surfactants include aminocarboxylates, alkyl betaines, and alkylimidazoline derivatives. Specifically, examples include lauramidopropyl betaine. The amphoteric surfactant may be only one type or two or more types.

[0058] Examples of ether-type nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyalkylene derivatives, polyoxyethylene phenyl ethers, and alkyl allyl ethers. Specifically, examples include polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, and polyoxyethylene octyl phenyl ether. Examples of ester / ether-type nonionic surfactants include sugar-type surfactants. Specifically, examples include sorbitan fatty acid esters, sorbitol, and polyoxyethylene sorbitan fatty acid esters. The nonionic surfactant may be only one type or two or more types.

[0059] Examples of the sugar-type surfactants include sucrose fatty acid esters, sorbitan acid esters, polysorbates, and the like. Specific examples of the sugar-type surfactant include sorbitol fatty acid esters such as sorbitol monolaurate, sorbitol monostearate, sorbitol monooleate, sorbitol trioleate, sorbitol tristearate, and sorbitol monoisostearate; sorbitan fatty acid esters such as sorbitan isostearate, sorbitan oleate, sorbitan caprylate, sorbitan dioleate, sorbitan distearate, sorbitan stearate, sorbitan sesquiisostearate, sorbitan sesquioleate, sorbitan sesquicaprylate, sorbitan sesquistearate, sorbitan triisostearate, sorbitan trioleate, sorbitan tristearate, sorbitan palmitate, sorbitan coconut fatty acid ester, sorbitan laurate, and sorbitan olive fatty acid ester; sucrose fatty acid esters such as sucrose isobutyrate acetate, sucrose octaacetate, sucrose oleate, sucrose distearate, sucrose dilaurate, sucrose stearate, sucrose tetraisostearate, sucrose tetrahydroxystearate, sucrose tristearate, sucrose tribehenate, sucrose trilaurate, sucrose triacetate tetrastearate, sucrose palmitate, sucrose hexaerucate, sucrose hexapalmitate, sucrose pentaerucate, sucrose pentahydroxystearate, sucrose polyoleate, sucrose polystearate, sucrose polysoybean oil fatty acid ester, sucrose polypalm fatty acid ester, sucrose polybehenate, sucrose polylaurate, sucrose polylinoleate, sucrose polymarine fatty acid ester, sucrose myristate, sucrose coconut fatty acid ester, sucrose laurate, sucrose ricinoleate, sucrose benzoate, sucrose acetate distearate, and sucrose acetate stearate; alkyl glucosides such as coconut oil fatty acid glucoside, lauryl glucoside, decyl glucoside, myristyl glucoside, palmityl glucoside, stearyl glucoside, and coco glucoside. These may be used alone or in combination of two or more.

[0060] As the sugar-type surfactant, sorbitan ester containing a nonpolar carboxylic acid (lipophilic group) bonded to a polar sorbitan group (hydrophilic group) by an ester bond is preferred. Further, polyoxyethylene derivatives of sorbitan ester and a plurality of polyoxyethylene oligomers chemically substituted on the sorbitan group are also preferred.

[0061] These polyoxyethylene derivatives of sorbitan ester are called polysorbate. Specifically, the polyoxyethylene derivative of sorbitan ester (also referred to as polysorbate) has the formula (I):

Chemical formula

[0062] Here, one of R 7 ~R 10 is a linear fatty acid moiety, and the other three of R 7 ~R 10 are each hydrogen. Also, w1, x1, y1, z1 are integers such that 10 < w1 + x1 + y1 + z1 < 40. Preferably 15 < w1 + x1 + y1 + z1 < 25, more preferably w1 + x1 + y1 + z1 = 20. Also, the linear fatty acid moiety is preferably (C=O)(CH2) a CH3. When the formula is (C=O)(CH2) b (CH)=(CH)(CH2) c CH3, the fatty acid moiety may alternatively contain a double bond along a hydrocarbon chain (i.e., may contain monounsaturation). Here, a is an integer from 10 to 25, preferably an integer from 12 to 18. Further, the linear fatty acid may contain an unsaturated bond. Also, b + c is an integer between 8 and 23, preferably an integer from 10 to 18. The number of unsaturated bonds may contain two or more unsaturations in the hydrocarbon chain, but the unsaturation is preferably 4 or less, more preferably 3 or less, and particularly preferably maintained at 0, 1, or 2.

[0063] Specific examples of polysorbates include polysorbate 20 (polyoxyethylene (20) sorbitan monolaurate), polysorbate 40 (polyoxyethylene (20) sorbitan monopalmitate), polysorbate 60 (polyoxyethylene (20) sorbitan monostearate), and polysorbate 80 (polyoxyethylene (20) sorbitan monooleate).

[0064] The 20, 40, 60, and 80 following "polysorbate" indicate the fatty acid moieties (the "lipophilic groups" of the molecule) attached to the polyoxyethylene sorbitan moiety (the "hydrophilic group" of the molecule). 20 is monolaurate, 40 is monopalmitate, 60 is monostearate, and 80 is monooleic acid (an example of a monounsaturated fatty acid moiety).

[0065] The name "polysorbate #" is assumed to have 20 oxyethylene moieties [-(CH2CH2O)-] added to sorbate.

[0066] In certain embodiments, the sugar-based surfactant can be or can include one or more of polysorbate 20, polysorbate 40, polysorbate 60, and / or polysorbate 80. For example, the surfactant can be polysorbate 60 or can include other polysorbates.

[0067] Also, instead of the above-described polysorbates, surfactants that are variants of the specific polysorbates described above can be used. For example, referring to formula (I), two, three, or all of R 7 ~R 10 can each be a straight-chain fatty acid moiety (the remainder of R 7 ~R 10 is hydrogen if there is any remainder). An example of this compound is where three of R 7 ~R 10 are the fatty acid moiety stearic acid, and R 7 ~R 10It contains polyoxyethylene sorbitan tristearate in which one of the others is hydrogen.

[0068] The melt flow rate (MFR) of the above lubricant (A) is preferably 100 g / 10 min or more, more preferably 500 g / 10 min or more. The upper limit is not particularly limited, but is usually 100,000 g / 10 min. If it is within the above range, the effect of improving processability will be better. In this specification, MFR is measured under the conditions of 190 °C and a load of 2.16 kgf in accordance with ASTM D 1238.

[0069] In the processing aid of the present disclosure, the content of the above lubricant (A) is preferably 1% by mass or more, more preferably 2% by mass or more, still more preferably 4% by mass or more, and preferably 98% by mass or less, more preferably 70% by mass or less, still more preferably 40% by mass or less, and most preferably 10% by mass or less.

[0070] The above resin (B) contains a structural unit represented by the following formula 1. Note that the above lubricant (A) preferably does not contain this structural unit. -X-(CR 1 R 2 ) n -Y-(CR 3 R 4 ) m -Z- (Formula 1) (In Formula 1, X is a divalent group which may have a single bond or a functional group, Y and Z are each independently a group composed of at least one selected from the group consisting of a single bond, -O-, -C(=O)-, -C(=O)O-, -OC(=O)O-, -C(=NR’)-, -C(=NR’)O-, -OC(=NR’)O-, -S-, -S(=O)-, -S(=O)O-, -OS(=O)O-, -S(=O)2-, -S(=O)2O-, -OS(=O)2O-, -P(=O)-, -P(=O)O-, -OP(=O)O-, -P(=O)2-, -P(=O)2O-, -OP(=O)2O-, -NR’-, and -C(OR’)R’- (wherein R’ is independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms at each occurrence).) R 1 、R 2 、R 3 and R 4 are each independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, n and m are each independently an integer from 0 to 10, At least one of X, Y, and Z is -C(=O)-, -C(=O)O-, -OC(=O)O-, or -C(OR’)R’-.

[0071] In the above formula 1, X is a divalent group composed of at least one selected from the group consisting of X 1 and X 2 is a divalent group composed of at least one selected from the group consisting of X X 1 is a group composed of at least one selected from the group consisting of -C(=O)-, -C(=NR’)-, -S(=O)2-, -NR’-, -CR’R’-, and -C(OR’)R’- (wherein R’ is independently, in each occurrence, a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms). X 2 is preferably an aromatic hydrocarbon group having 1 to 12 carbon atoms which may have a substituent.

[0072] In the above formula 1, X is more preferably a divalent group containing at least one selected from the group consisting of -C(=O)-, -CR’R’-, and -C(OR’)R’- (wherein R’ is independently, in each occurrence, a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms).

[0073] In the above formula 1, R’ is preferably, in each occurrence, independently a hydrogen atom or a hydrocarbon group having 1 to 7 carbon atoms, more preferably a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, and still more preferably a hydrogen atom or a hydrocarbon group having 1 carbon atom.

[0074] In the above formula (1), Y and Z are each independently preferably a group composed of at least one selected from the group consisting of a single bond, -O-, -C(=O)-, -C(=O)O-, -C(=NR’)-, -C(=NR’)O-, -S-, -S(=O)2-, -S(=O)2O-, -NR’-, and -C(OR’)R’- (wherein R’ is independently at each occurrence a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms).

[0075] In the above formula (1), Y and Z are each independently preferably a group composed of at least one selected from the group consisting of a single bond, -O-, -C(=O)-, and -C(=O)O-.

[0076] In the above formula (1), R 1 , R 2 , R 3 and R 4 are each independently preferably a hydrogen atom or a hydrocarbon group having 1 to 7 carbon atoms, more preferably a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, and even more preferably a hydrogen atom or a hydrocarbon group having 1 carbon atom.

[0077] n and m are each independently preferably an integer from 0 to 8, more preferably an integer from 0 to 6, even more preferably an integer from 0 to 4, and particularly preferably an integer from 0 to 2.

[0078] Examples of the above resin (B) include polylactic acid (PLA), polybutylene succinate (PBS), ethylene-vinyl alcohol copolymer (EVOH), polybutylene succinate adipate (PBSA), and the like. The resin (B) is preferably at least one selected from the group consisting of PLA, PBS, EVOH, and PBSA, more preferably at least one selected from the group consisting of PLA, PBS, and EVOH, and even more preferably at least one selected from the group consisting of PLA and EVOH.

[0079] In addition, the resin (B) may contain structural units other than the structural unit represented by Formula 1. The structural units that may be contained in addition to the structural unit represented by Formula 1 are, for example, glycol compounds such as ethylene glycol, propylene glycol, butanediol, heptanediol, hexanediol, octanediol, nonanediol, decanediol, 1,4-cyclohexanedimethanol, neopentyl glycol, glycerin, pentaerythritol, bisphenol A, polyethylene glycol, polypropylene glycol, and polytetramethylene glycol; dicarboxylic acids such as oxalic acid, adipic acid, sebacic acid, azelaic acid, dodecanedioic acid, malonic acid, glutaric acid, cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, naphthalenedicarboxylic acid, bis(p-carboxyphenyl)methane, anthracenedicarboxylic acid, 4,4'-diphenyl ether dicarboxylic acid, 5-sodium sulfoisophthalic acid, and 5-tetrabutylphosphonium isophthalic acid; hydroxycarboxylic acids such as glycolic acid, hydroxypropionic acid, hydroxybutyric acid, hydroxyvaleric acid, hydroxycaproic acid, and hydroxybenzoic acid; lactones such as caprolactone, valerolactone, propiolactone, undecalactone, and 1,5-oxepan-2-one; and the like.

[0080] In the above resin (B), the content of the structural unit represented by Formula 1 is preferably 0.1% by mass or more, more preferably 1% by mass or more, still more preferably 10% by mass or more, and particularly preferably 20% by mass or more. Also, it is preferably 99.9% by mass or less, more preferably 99% by mass or less, still more preferably 95% by mass or less.

[0081] The ethylene content of the above ethylene-vinyl alcohol copolymer is preferably 10 mol% or more, more preferably 20 mol% or more, still more preferably 30 mol% or more, and preferably 60 mol% or less, more preferably 50 mol% or less, and still more preferably 40 mol% or less. Within the above range, the effect of improving processability is better. In this specification, the ethylene content is determined by nuclear magnetic resonance (NMR) method.

[0082] The above ethylene-vinyl alcohol copolymer is preferably obtained by saponifying an ethylene-vinyl ester copolymer. Among them, those obtained by saponifying an ethylene-vinyl acetate copolymer are particularly preferred.

[0083] The saponification degree of the above ethylene-vinyl alcohol copolymer is preferably 80 to 100 mol%.

[0084] When copolymerizing ethylene and vinyl acetate, other vinyl fatty acid esters (such as vinyl propionate, vinyl pivalate, etc.) can also be used in combination. In addition, the ethylene-vinyl alcohol copolymer can also contain 0.0002 to 0.2 mol% of a vinyl silane compound as a copolymerization component. Here, examples of the vinyl silane compound include vinyl trimethoxysilane, vinyl triethoxysilane, vinyl tri(β-methoxy-ethoxy)silane, and γ-methacryloxypropyl methoxysilane. Among them, vinyl trimethoxysilane and vinyl triethoxysilane are preferably used.

[0085] When copolymerizing ethylene and vinyl acetate, monomers other than the above-mentioned vinyl fatty acid esters and vinyl silane compounds, for example, α-olefins such as propylene, isobutylene, α-octene, and α-dodecene; unsaturated acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, and itaconic acid or their anhydrides, salts, or mono- or dialkyl esters, etc.; nitriles such as acrylonitrile and methacrylonitrile; amides such as acrylamide and methacrylamide; olefin sulfonic acids such as ethylene sulfonic acid, allyl sulfonic acid, and methallyl sulfonic acid or their salts; alkyl vinyl ethers, vinyl ketones, N-vinyl pyrrolidone, vinyl chloride, vinylidene chloride, etc. can also coexist in small amounts.

[0086] The melting point of the above resin (B) is preferably 65°C or higher, more preferably 70°C or higher, still more preferably 75°C or higher, and even more preferably 80°C or higher, and is preferably 190°C or lower, more preferably 185°C or lower, still more preferably 180°C or lower. Within the above ranges, the effect of improving processability is better. In this specification, the melting point is the temperature corresponding to the maximum value in the melting heat curve when the temperature is raised at a rate of 10°C / min using a differential scanning calorimetry (DSC) apparatus.

[0087] The melt flow rate (MFR) of the above resin (B) is preferably 0.001 g / 10 min or more, more preferably 0.01 g / 10 min or more, still more preferably 0.05 g / 10 min or more, even more preferably 0.1 g / 10 min or more, particularly preferably 0.5 g / 10 min or more, and is preferably 500 g / 10 min or less, more preferably 300 g / 10 min or less, still more preferably 150 g / 10 min or less, even more preferably 40 g / 10 min or less, even more preferably 20 g / 10 min or less, and particularly preferably 10 g / 10 min or less. Within the above ranges, the effect of improving processability is better. In this specification, the MFR is measured under the conditions of 190°C and a load of 2.16 kgf in accordance with ASTM D 1238.

[0088] From the viewpoint of improving processability, the weight average molecular weight of the above resin (B) is preferably 80,000 or more, more preferably 100,000 or more, and from the same viewpoint, it is preferably 400,000 or less, more preferably 350,000 or less. The weight average molecular weight of the above resin (B) can be determined by gel permeation chromatography (GPC) using chloroform as the solvent, a high-temperature SEC column (GMHHR-H series) manufactured by Tosoh Corporation for the column, a flow rate of 1.0 mL / min, a column temperature of 40°C, a differential refractive index detector (RI) for the detector, and polystyrene having a known molecular weight as a reference for conversion.

[0089] In the processing aid of the present disclosure, the content of the resin (B) is preferably 1% by mass or more, more preferably 30% by mass or more, still more preferably 60% by mass or more, and preferably 99% by mass or less, more preferably 98% by mass or less, still more preferably 96% by mass or less.

[0090] The processing aid of the present disclosure may contain components other than the lubricant (A) and the resin (B). Examples of other components include other additives (E). Examples of the other additives (E) include at least one synergist selected from the group consisting of polyols having a melting point of 80°C or lower, polycaprolactone, silicone, and polyamide-polyether block copolymers.

[0091] The melting point of the polyol may be 80°C or lower, preferably 75°C or lower, more preferably 70°C or lower, still more preferably 68°C or lower, and preferably 10°C or higher, more preferably 20°C or higher, still more preferably 25°C or higher. Within the above range, the effect of improving processability is better.

[0092] The polyol can be represented, for example, by A[(OR 11 ) x2 OR 12 y2 In the formula, A is usually an alkylene having one or more ether bonds, y2 is 2 or 3, and (OR 11 ) x2 is a poly(oxyalkylene) chain having a plurality (x2) of oxyalkylene groups OR 11 . Each R 11 is independently a C2-C5 alkylene, and in some embodiments, a C2-C3 alkylene. R 12 is hydrogen, alkyl, aryl, arylalkenyl, alkylarylenyl, -C(O)-alkyl, -C(O)-aryl, -C(O)-arylalkenyl or -C(O)-alkylarylenyl, and -C(O)- is bonded to the O of OR 12 . x2 is from 10 to 230,000. ​

[0093] The above polyol is R 11 is a homopolymer of poly(oxyethylene) where -CH2CH2-, or R 11 is a homopolymer of poly(oxypropylene) where -C3H6- etc. can be used.

[0094] The above polyol is a chain of randomly distributed oxyalkylene groups (for example, -OC2H4- and -OC3H6- units which are copolymers), or an alternating block consisting of repeating oxyalkylene groups (for example, (-OC2H4-) a1 block and (-OC3H6-) b1 block, and a1 + b1 is a polymer having a chain of 10 to 230,000) can also be used.

[0095] In some embodiments of the above polyol, A is ethylene, -CH2-CH(-)-CH2- (derived from glycerol), CH3CH2C(CH2-)3 (derived from 1,1,1-trimethylolpropane), poly(oxypropylene), -CH2CH2-O-CH2CH2- or -CH2CH2-O-CH2CH2-O-CH2CH2-, and R 2 is hydrogen, methyl, butyl, phenyl, benzyl, acetyl, benzoyl or stearyl.

[0096] The above polyol is a polyester prepared from a dicarboxylic acid and a poly(oxyalkylene) polymer represented by A[(OR 11 ) x2 OR 12 y2 where A, R 11 and x2 are as defined above, and R 12 is hydrogen and y2 is 2 may also be in the form.

[0097] The above polyol may be used alone or in combination of two or more. From the viewpoint of excellent improvement effect on processability, polyethylene glycol and polyethylene oxide are preferred, and polyethylene glycol is particularly preferred.​

[0098] The number average molecular weight (Mn) of the above polyethylene glycol is preferably 1,000 or more, more preferably 3,000 or more, still more preferably 5,000 or more, and is preferably 50,000 or less, more preferably 45,000 or less, still more preferably 40,000 or less. If it is within the above range, the effect of improving processability will be better. In this specification, the number average molecular weight is determined by calculation from the hydroxyl value measured in accordance with JIS K0070.

[0099] The viscosity average molecular weight (Mv) of the above polyethylene oxide is preferably 100,000 or more, more preferably 120,000 or more, still more preferably 140,000 or more, and is preferably 10,000,000 or less, more preferably 1,600,000 or less, still more preferably 500,000 or less. If it is within the above range, the effect of improving processability will be better. In this specification, the viscosity average molecular weight is calculated as follows. Using an Ostwald viscometer, the specific viscosity ηsp of aqueous solutions with various polymer concentrations c (g / dl) in pure water is measured at 35°C, and [η] is calculated by extrapolating the polymer concentration c to 0 based on the relationship between the reduced viscosity (ηsp / c) obtained by dividing the specific viscosity by the polymer concentration and the polymer concentration c. [η] is inserted into the following formula to calculate the viscosity average molecular weight M. Formula: [η]=6.4×10 -5 M 0.82

[0100] The above polycaprolactone may be a homopolymer of ε-caprolactone or a modified polycaprolactone. Examples of the modified polycaprolactone include those modified by coexisting with 1,4-butanediol or the like when ring-opening polymerizing ε-caprolactone, and those with the terminals of the polymer modified with ether, ester groups, or the like.

[0101] The weight average molecular weight (Mw) of the above polycaprolactone is preferably 2,000 or more, more preferably 10,000 or more, still more preferably 25,000 or more, and is preferably 100,000 or less, more preferably 95,000 or less, still more preferably 90,000 or less. If it is within the above range, the effect of improving processability will be better. In this specification, the weight average molecular weight is measured by polystyrene conversion using gel permeation chromatography (GPC) method.

[0102] The melting point of the above polycaprolactone is preferably 80 °C or less, more preferably 75 °C or less, still more preferably 70 °C or less, even more preferably 68 °C or less, and is preferably 10 °C or more, more preferably 20 °C or more, still more preferably 45 °C or more. If it is within the above range, the effect of improving processability will be better.

[0103] The above silicone can in principle be all organosilicon compounds known to those skilled in the art by the term silicone polymer. An appropriate definition of silicone can be found in Winnacker / Kuchler: "Chemische Technik" [Chemical Technology], R. Dittmeyer, W. Keim, G. Kreysa, A. Oberholz (editors), Volume 5: "Organische Zwischenverbindungen, Polymere" [Organic Intermediates, Polymers], chapter: "Silicones", Wiley-VCH, Weinheim, 2005.

[0104] Silicone can be a substituted or unsubstituted linear oligo- or polydiorganosiloxane, a branched silicone polymer, a silicone resin or a cross-linked silicone polymer. Naturally, mixtures consisting of various silicone polymers can also be used. As already mentioned, silicone-containing copolymers, for example polyether-functional silicones, silicones containing urea or urethane units or silicone block copolymers with organic polymers can also be used. For the purpose of better additivity, the use of high molecular weight polydiorganosiloxanes which also contain non-silicone components, for example fillers such as particulate silicic acid, chalk, talc and sheet silicates, is particularly preferred.

[0105] Preferably, the silicone polymer corresponds to formula A, [R 13 3SiO 1 / 2 a2 [SiR 13 2O 2 / 2 b2 [R 13 SiO 3 / 2 c2 [SiO 4 / 2 d2 , where R 13 is hydrogen, -OH or an unsubstituted or substituted C1 to C18 hydrocarbon residue, and a2, b2, c2, d2 each mean 0 or an integer, and a2 + b2 + c2 + d2 is an integer from 5 to 15000.

[0106] The C1 to C18 hydrocarbon residue R 13 ​​​​Examples include alkyl residues such as methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl residues, hexyl residues such as n-hexyl residues, heptyl residues such as n-heptyl residues, octyl residues such as n-octyl residues and isooctyl residues such as 2,2,4-trimethylpentyl residues, nonyl residues such as n-nonyl residues, decyl residues such as n-decyl residues, cycloalkyl residues such as cyclopentyl residues, cyclohexyl residues, 4-ethylcyclohexyl residues and cycloheptyl residues, norbornyl residues and methylcyclohexyl residues. Among the alkyl residues, C1 to C6 residues such as methyl and ethyl residues, particularly methyl residues, are preferred.

[0107] R 13 Examples of the residue R also include unsaturated C1 to C18 hydrocarbon residues such as alkenyl residues such as vinyl residues, 2-propen-2-yl residues, allyl residues, 3-buten-1-yl residues, 5-hexen-1-yl residues, 10-undecen-1-yl residues, and cycloalkenyl residues (2-cyclohexenyl residues, 3-cyclohexenyl residues, cyclopentadienyl residues, 2-(cyclohex-3-en-1-yl)ethyl residues); aryl residues such as phenyl residues, biphenylyl residues and naphthyl residues; alkaryl residues such as o-, m- and p-tolyl residues and phenethyl residues (2-phenylethyl residues, 1-phenylethyl residues) and aralkyl residues such as benzyl residues. Preferred unsaturated C1 to C18 hydrocarbon residues R 13 are vinyl residues and phenyl residues.

[0108] residue R 13 Examples of the substituted hydrocarbon residue as the residue R include halogenated hydrocarbons such as chloromethyl residues, 3-chloropropyl residues, 3-bromopropyl residues, 3,3,3-trifluoropropyl residues and 5,5,5,4,4,3,3-heptafluoropentyl residues, and chlorophenyl residues, dichlorophenyl residues and trifluorotolyl residues.

[0109] Residue R 13 preferably binds to the silicone polymer represented by formula A via a Si-C bond, but can also bind to the silicone polymer via an oxygen atom -O-.

[0110] R 13 preferably has 1 to 6 carbon atoms. Ethyl residue, phenyl residue, vinyl residue and methyl residue are particularly preferred.

[0111] Preferably, a2 + b2 + c2 + d2 means a number of at least 10, more preferably at least 100, particularly preferably at least 1000 and at most 15000, more preferably at most 10000, particularly preferably at most 7000.

[0112] Preferably, c2 + d2 means <0.1×(a2 + b2 + c2 + d2), particularly c2 + d2 <0.05×(a2 + b2 + c2 + d2).

[0113] Preferably, all residues R 13 at least 50%, more preferably at least 70%, particularly preferably at least 80% of which are methyl residues.

[0114] In principle, all silicone polymers corresponding to formula A can be used. However, a silicone polymer having a dynamic viscosity exceeding 1000 mPa·s, preferably measured in accordance with DIN EN ISO 3219:1994 and DIN 53019, using an Anton Paar "MCR 302" rheometer with a plate-cone system (cone CP50-2) having an opening angle of 2° and a diameter of 50 mm, a measurement temperature of 25.00 °C ± 0.05 °C, and a shear rate of 1 sec-1 is preferred.

[0115] Among silicones, silicone polymers having a very high molecular weight, for example, UHMW polysiloxanes (ultra-high molecular weight; described in K.J. Ryan et al., Journal of Vinyl & Additive Technology, March 2000, Vol. 6, No. 1, pp. 7-19) may be used.

[0116] The degree of polymerization of UHMW polysiloxane is in the range of >1000 to about 14000, which corresponds to a number average molecular weight between 74 kg / mol and 1000 kg / mol.

[0117] A typical UHMW polysiloxane preferably has a dynamic viscosity between 10 kPa·s and 50 kPa·s, preferably between 15 kPa·s and 30 kPa·s, measured with an air-suspended rotary rheometer according to DIN EN ISO 3219:1994 and DIN 53019, where a plate-plate system (diameter 25 mm) with a measurement gap of 0.5 mm is used. The measurement temperature is 25.00 °C + / - 0.1 °C. The shear rate gradient is 0.1 sec -1 -1. The viscosity description represents the arithmetic mean of three individual measurements performed independently.

[0118] Among the above UHMW polysiloxanes, high molecular weight polydimethylsiloxanes having a dynamic viscosity between 1 kPa·s and 50 kPa·s, preferably between 10 and 40 kPa·s, particularly preferably between 15 and 30 kPa·s (preferably measured by the above method) are particularly preferred because they are inexpensive and effective.

[0119] The above-mentioned UHMW polysiloxane includes commercially available UHMW polysiloxanes such as MULTIBASE® MB50-001 and MULTIBASE® MB50-002 manufactured by Dupont, GENIOPLAST® PELLET S, GENIOPLAST® PELLET P PlUS, GENIOPLAST® PE50S08, GENIOPLAST® PP50S12 manufactured by Asahi Kasei Wacker Silicone, and their mixtures. MB50-002 and GENIOPLAST® PELLET S are preferred.

[0120] Silicone polymers are commercially available in the form of pellets / granules or masterbatches and can be used immediately, for example, they can be mixed with thermoplastic plastic granules before further processing.

[0121] The above-mentioned polyamide-polyether block copolymer is a copolymer having a polyamide block and a polyether block in the polymer backbone. In the present disclosure, such a block copolymer having a polyamide block and a polyether block can also be referred to as a "polyamide / polyether block copolymer". Also, it can be abbreviated as "PEBA copolymer" or "PEBA". In some embodiments of the present disclosure, the PEBA copolymer can be represented by the following general formula.

Chemical formula

[0122] Here, PA is a polyamide block, PE is a polyether block, p represents the length of the PEBA copolymer, and represents the total number of polyamide and polyether blocks. In some embodiments of the present disclosure, the PEBA copolymer can be represented by the following general formula.

Chemical formula

[0123] Here, EG is the first unspecified end group, B is the unspecified crosslinking group, and EG * is the second unspecified end group, and EG, B, and EG * are determined by the synthesis method used to produce the PEBA copolymer. Here, n2 represents the length of the polyamide block, x3 represents the length of the amide component 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. In some embodiments of the present disclosure, the PEBA copolymer can be represented by the following general formula. [Chemical formula]

[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 block in the above PEBA copolymer is derived from polyamide-12 (PA-12), polyamide-11 (PA-11), polyamide-6 (PA-6), or polyamide-66 (PA-66).

[0126] The weight average molecular weight (e.g., Mw and Mn) of the PEBA copolymer can be measured, for example, by gel permeation chromatography (i.e., size exclusion chromatography) using a narrow molecular weight polymer standard with techniques known in the art.

[0127] In an embodiment, the number average molecular weight Mn of the polyamide block in the PEBA copolymer is from about 100 to about 15,000 g / mol, or from about 300 to about 15,000 g / mol, or from about 600 to about 10,000 g / mol, or from about 600 to about 5,000 g / mol. The number average molecular weight Mn of the polyether block in the PEBA copolymer is from about 100 to about 15,000 g / mol, from about 100 to about 10,000 g / mol, from about 100 to about 6,000 g / mol, from about 100 to about 3,000 g / mol, from about 200 to about 6,000 g / mol, from about 200 to about 3,000 g / mol, from about 250 to about 2,000 g / mol, from about 750 to about 3,500 g / mol, or from about 1,000 to about 3,000 g / mol.

[0128] The number average molecular weight Mn of the PEBA copolymer is from 10,000 to 500,000 g / mol, including sub-ranges within this range and any numbers within this range. For example, in embodiments of the present disclosure, the number average molecular weight Mn of the PEBA copolymer is from 10,000 to 400,000 g / mol, or from 10,000 to 300,000 g / mol, 10,000 to 250,000 g / mol, or from 15,000 to 300,000 g / mol, or from 20,000 to 300,000 g / mol, or from 15,000 to 200,000 g / mol, or from 20,000 to 200,000 g / mol, or from 30,000 to 250,000 g / mol, or from about 25,000 to about 75,000 g / mol, or from about 50,000 to about 75,000 g / mol, or from about 100,000 to about 150,000 g / mol. The number average molecular weight Mn of the PEBA copolymer is at least 10,000 g / mol, at least 20,000 g / mol, at least 25,000 g / mol, more than 25,000 g / mol, at least 30,000 g / mol, more than 30,000 g / mol, at least 35,000 g / mol, more than 35,000 g / mol, at least 50,000 g / mol, or more than 50,000 g / mol.

[0129] In an embodiment, the weight average molecular weight Mw of the PEBA copolymer is from 25,000 to 500,000 g / mol, including sub-ranges within this range and any numbers within this range. For example, in embodiments of the present disclosure, the weight average molecular weight Mw of the PEBA copolymer is from about 100,000 to about 250,000 g / mol, or from about 100,000 to about 150,000 g / mol, or from about 125,000 to about 150,000 g / mol. The polyamide and polyether blocks within the above PEBA copolymer can be randomly distributed.

[0130] The above PEBA copolymer includes a polyamide block and a polyether block, and the polyamide block may account for at least 50% by mass of the copolymer. The above PEBA copolymer includes a polyamide block and a polyether block, and the polyether block may account for at least 50% by mass of the copolymer. Further, the PEBA copolymer includes a polyamide block and a polyether block, and the molar ratio of the polyamide block to the polyether block may be in the range of 1:3 to 3:1, or 1:2 to 2:1, or 3:2 to 1:3, or 2:3 to 3:1, or about 1:1.

[0131] By reacting the above polyamide and polyether block precursors, a PEBA copolymer having polyamide blocks and polyether blocks can be prepared. For example, lactam, polyether diol, and a chain-limiting diacid are reacted together in the presence of a small amount of water to obtain a PEBA copolymer having polyamide blocks and polyether blocks with variable lengths and a statistically random distribution within the block copolymer chains. The above polyether block is derived from poly(oxyethylene), poly(oxypropylene), or poly(tetramethylene ether) glycol, and each may be co-condensed with a polyamide block containing carboxylic acid chain ends in its natural state. During the polycondensation reaction, a chain limiter is also present, which can give a PEBA copolymer containing polyamide blocks and polyether blocks randomly distributed in the block copolymer. The above polyether block is derived from poly(oxyethylene), poly(oxypropylene), or poly(tetramethylene ether) glycol, which are first converted to polyether diamines by amination and then co-condensed with polyamide blocks containing carboxylic acid chain ends. During the polycondensation reaction, a chain limiter is also present, which can give a PEBA copolymer containing polyamide blocks and polyether blocks randomly distributed in the block copolymer. The above polyether block can be derived from poly(oxyethylene), also known as polyethylene glycol (PEG). The above polyether block can be derived from poly(oxypropylene), also known as polypropylene glycol (PPG). The above polyether block can be derived from poly(tetramethylene ether) glycol (PTMG), also known as polytetramethylene oxide (PTMEO) or polytetrahydrofuran (PTHF).

[0132] The above PEBA copolymer contains i) a polyamide block selected from polyamide-12 (PA-12), polyamide-11 (PA-11), polyamide-6 (PA-6), or a mixture thereof, and ii) a polyether block selected from polyethylene glycol (PEG), polypropylene glycol (PPG), polytetrahydrofuran (PTHF), or a mixture thereof.

[0133] The above-mentioned PEBA copolymer comprises: i) a polyamide block selected from polyamide-12 (PA-12), polyamide-11 (PA-11), polyamide-6 (PA-6), or a mixture thereof; and ii) a polyether block which is polyethylene glycol (PEG). In one embodiment of the present disclosure, the PEBA copolymer comprises: i) a polyamide block which is polyamide-12 (PA-12); and ii) a polyether block which is polyethylene glycol (PEG).

[0134] The above-mentioned PEBA copolymer comprises 10 to 20 polyamide blocks and 10 to 20 polyether blocks.

[0135] The above-mentioned PEBA copolymer comprises only one type of polyamide block and one type of polyether block.

[0136] The above-mentioned PEBA copolymer comprises: i) a polyamide block which is polyamide-12 (PA-12); and ii) a polyether block which is polyethylene glycol (PEG), wherein the polyamide-12 block accounts for about 30% to 70% by mass of the copolymer, and the polyethylene glycol block accounts for about 70% to 30% by mass of the copolymer.

[0137] The above-mentioned PEBA copolymer comprises: i) a polyamide block which is polyamide-12 (PA-12); and ii) a polyether block which is polyethylene glycol (PEG), wherein the polyamide-12 block accounts for about 40% to 60% by mass of the copolymer, and the polyethylene glycol block accounts for about 60% to 40% by mass of the copolymer.

[0138] The above-mentioned PEBA copolymer comprises: i) a polyamide block which is polyamide-12 (PA-12); and ii) a polyether block which is polyethylene glycol (PEG), wherein the polyamide-12 block represents about 45% by mass of the copolymer, and the polyethylene glycol block represents about 55% by mass of the copolymer.

[0139] The above-mentioned PEBA copolymer contains: i) 10 to 20 polyamide blocks which are polyamide-12 (PA-12), and ii) 10 to 20 polyether blocks which are polyethylene glycol (PEG).

[0140] The above-mentioned PEBA copolymer contains: i) a polyamide block which is polyamide-12 (PA-12), and ii) a polyether block which is polyethylene glycol (PEG), and has a number average molecular weight Mn of about 25,000 to about 75,000 g / mol.

[0141] The above-mentioned PEBA copolymer contains: i) a polyamide block which is polyamide-12 (PA-12), and ii) a polyether block which is polyethylene glycol (PEG), and has a number average molecular weight Mn of about 50,000 to about 75,000 g / mol. The above-mentioned PEBA copolymer contains: i) a polyamide block which is polyamide-12 (PA-12) and ii) a polyether block which is polyethylene glycol (PEG), and has a number average molecular weight Mn of about 66,100 g / mol.

[0142] The above-mentioned PEBA copolymer contains: i) a polyamide block which is polyamide-12 (PA-12), and ii) a polyether block which is polyethylene glycol (PEG), and has a weight average molecular weight Mw of about 100,000 to about 150,000 g / mol.

[0143] The above-mentioned PEBA copolymer contains: i) a polyamide block which is polyamide-12 (PA-12), and ii) a polyether block which is polyethylene glycol (PEG), and has a weight average molecular weight Mw of about 125,000 to about 150,000 g / mol.

[0144] The above-mentioned PEBA copolymer contains: i) a polyamide block which is polyamide-12 (PA-12) and ii) a polyether block which is polyethylene glycol (PEG), and has a weight average molecular weight Mw of about 134,000 g / mol.

[0145] In one embodiment of the present disclosure, the PEBA copolymer comprises i) a polyamide block that is polyamide-6 (PA-6), and ii) a polyether block that is polyethylene glycol (PEG). The above PEBA copolymer comprises i) a polyamide block that is polyamide-6 (PA-6) and ii) a polyether block that is polyethylene glycol (PEG), wherein the polyamide-6 block represents from about 30% to 60% by mass of the copolymer, and the polyethylene glycol block represents from about 70% to 40% by mass of the copolymer.

[0146] The above PEBA copolymer comprises i) a polyamide block that is polyamide-6 (PA-6) and ii) a polyether block that is polyethylene glycol (PEG), wherein the polyamide-6 block represents from about 50% to 35% by mass of the copolymer, and the polyethylene glycol block represents from about 50% to 65% by mass of the copolymer.

[0147] The above PEBA copolymer comprises i) from 10 to 20 polyamide blocks that are polyamide-6 (PA-6), and ii) from 10 to 20 polyether blocks that are polyethylene glycol (PEG).

[0148] The above PEBA copolymer comprises i) a polyamide block that is polyamide-11 (PA-11), and ii) a polyether block that is polyethylene glycol (PEG). In one embodiment of the present disclosure, the PEBA copolymer comprises i) a polyamide block that is polyamide-12 (PA-12), and ii) a polyether block that is polytetrahydrofuran (PTHF).

[0149] The above-mentioned PEBA copolymer contains i) a polyamide block which is polyamide-12 (PA-12), and ii) a polyether block which is polytetrahydrofuran (PTHF), where the polyamide-12 block represents from about 75% to 10% by mass of the copolymer, and the polytetrahydrofuran block represents from about 25% to 90% by mass of the copolymer.

[0150] The above-mentioned PEBA copolymer contains i) a polyamide block which is polyamide-12 (PA-12), and ii) a polyether block which is polytetrahydrofuran (PTHF), where the polyamide-12 block represents from about 80% to 60% by mass of the copolymer, and the polytetrahydrofuran block represents from about 20% to 40% by mass of the copolymer.

[0151] The above-mentioned PEBA copolymer contains i) a polyamide block which is polyamide-12 (PA-12), and ii) a polyether block which is polytetrahydrofuran (PTHF), where the polyamide-12 block represents from about 40% to 60% by mass of the copolymer, and the polytetrahydrofuran block represents from about 60% to 40% by mass of the copolymer.

[0152] The above-mentioned PEBA copolymer contains i) a polyamide block which is polyamide-12 (PA-12), and ii) a polyether block which is polytetrahydrofuran (PTHF), where the polyamide-12 block represents from about 30% to 10% by mass of the copolymer, and the polytetrahydrofuran block represents from about 70% to 90% by mass of the copolymer. The above-mentioned PEBA copolymer contains i) 10 to 20 polyamide blocks which are polyamide-12 (PA-12), and ii) 10 to 20 polyether blocks which are polytetrahydrofuran (PTHF).

[0153] The above-mentioned PEBA copolymer includes i) a polyamide block that is polyamide-12 (PA-12) and ii) a polyether block that is polytetrahydrofuran (PTHF), and has a number-average molecular weight Mn of from about 25,000 to about 75,000 g / mol. The above-mentioned PEBA copolymer includes i) a polyamide block that is polyamide-12 (PA-12) and ii) a polyether block that is polytetrahydrofuran (PTHF), and has a number-average molecular weight Mn of from about 40,000 to about 60,000 g / mol. In an embodiment of the present disclosure, the PEBA copolymer includes i) a polyamide block that is polyamide-12 (PA-12) and ii) a polyether block that is polytetrahydrofuran (PTHF), and has a number-average molecular weight Mn of about 50,000 g / mol.

[0154] The above-mentioned PEBA copolymer includes i) a polyamide block that is polyamide-6 (PA-6) and ii) a polyether block that is polytetrahydrofuran (PTHF). The above-mentioned PEBA copolymer includes i) a polyamide block that is polyamide-11 (PA-11) and ii) a polyether block that is polytetrahydrofuran (PTHF). The above-mentioned PEBA copolymer is a commercially available elastomer and is sold under the trade name PEBAX®.

[0155] The above-mentioned PEBA copolymer is a commercially available elastomer selected from the group consisting of: PEBAX 2533 SA 01, PEBAX 2533 SA 01 MED, PEBAX 2533 SD 02, PEBAX 3533 SA 01, PEBAX 3533 SA 01 MED, PEBAX 3533 SP01, PEBAX 4011, PEBAX 4033 SA 01, PEBAX 4033 SA 01 MED, PEBAX 4033 SP01, PEBAX 4533 SA 01, PEBAX 4533 SA 01 MED, PEBAX 4533 SP01, PEBAX 5513 SA 01, PEBAX 5513 SP01, PEBAX 5533 SA 01, PEBAX 5533 SA 01 MED, PEBAX 5533 SN 70 BLACK, PEBAX 5533 SP01, PEBAX SA 01, PEBAX 6333 SA 01 MED, PEBAX SP01, PEBAX 6333 SP01, PEBAX 6333 SA 01, PEBAX, PEBAX 3533 SA 01, PEBAX 3533 SA 01 MED, PEBAX 3533 SP01, PEBAX 4011 SA 01, PEBAX 4033 SA 01 MED, PEBAX 4033 SP01, PEBAX 4033 SA 01 MED, PEBAX Clear 2533, PEBAX ES 2533 UV, PEBAX MH 2533, PEBAX MH2030, PEBAX MV 5513 SA 01, PEBAX MV 5513 SA 01 MED, PEBAX MV 5533 SP01, PEBAX MV 5533, PEBAX MV 5533 SP01, PEBAX RNEW (registered trademark) 30R51 SA 01, PEBAX RNEW 35R53 SP01, PEBAX RNEW 70R53 SP01, PEBAX RNEW 55R53 SP01, PEBAX RNEW 63R53 SP01, PEBAX RNEW 70R53 SP01, PEBAX RNEW 70R53 SP01, PEBAX, PEBAX RNEW 72R53 SP01, PEBAX RNEW 80R53 SP 02 and mixtures thereof. The above-mentioned PEBA copolymer is a commercially available elastomer and is sold under the trade names VESTAMID® or VESTAMID E.

[0156] The above-mentioned PEBA copolymer is a commercially available elastomer selected from the group consisting of VESTAMID D, VESTAMID DX, VESTAMID E, VESTAMID EX, VESTAMID Care, VESTAMID Care ML, VESTAMID Care ME, VESTAMID Care ME-B, VESTAMID L, VESTAMID LX, VESTAMID NRG, VESTAMID Terra, VESTAMID X, and mixtures thereof. Among them, Pebax MV1072 is preferred.

[0157] The above-mentioned PEBA copolymer can be used in the form of a semi-solid or viscous liquid, or as a powder, pellet or granule.

[0158] In the processing aid of the present disclosure, the content of the above-mentioned synergist is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, still more preferably 1% by mass or more, and is preferably 99% by mass or less, more preferably 70% by mass or less, still more preferably 40% by mass or less.

[0159] In the processing aid of the present disclosure, the total amount of the above-mentioned lubricant (A) and the above-mentioned resin (B) and the mass ratio of the above-mentioned synergist (lubricant (A) + resin (B): synergist) are preferably 99.9:0.1 to 10:90. The above mass ratio is more preferably 99.5:0.5 to 30:70, still more preferably 99:1 to 50:50, and particularly preferably 98:2 to 60:40.

[0160] As other components, for example, an anti-sticking agent; an ultraviolet absorber; a flame retardant; a reinforcing material such as glass fiber and glass powder; a stabilizer such as mineral and flake; a lubricant such as silicone oil and molybdenum disulfide; a pigment such as titanium dioxide and valve handle; a conductive agent such as carbon black; an impact resistance improver such as rubber; an antioxidant such as hindered phenol type and phosphorus type; a nucleating agent such as metal salt and acetal of sorbitol, and an anti-blocking agent can also be used.

[0161] In the processing aid of the present disclosure, the mass ratio of the lubricant (A) to the resin (B) (lubricant (A): resin (B)) is preferably 1:99 to 99:1, more preferably 2:98 to 40:60, and most preferably 4:96 to 10:90.

[0162] From the viewpoint of excellent storage stability, it is preferable to use a plurality of resins (B). In this case, it is preferable to use EVOH (resin (B1)) and a resin (B) other than EVOH (resin (B2)) in combination. The resin (B2) is not particularly limited, but is preferably PLA or PBS, and more preferably PLA. That is, the resin (B) preferably uses EVOH in combination with PLA and / or PBS, and more preferably uses EVOH and PLA in combination.

[0163] The mass ratio of the lubricant (A), the resin (B1), and the resin (B2) (lubricant (A): resin (B1): resin (B2)) is preferably 1 to 98:1 to 98:1 to 98, more preferably 2 to 70:5 to 73:25 to 93, and most preferably 4 to 18:10 to 24:72 to 86.

[0164] In the processing aid of the present disclosure, the total content of the lubricant (A), the resin (B), and the synergist is preferably 25% by mass or more, more preferably 35% by mass or more, still more preferably 55% by mass or more, and particularly preferably 85% by mass.

[0165] The processing aid of the present disclosure preferably contains substantially no fluorine. "Substantially free of fluorine" means that the fluorine content in the processing aid is 10 ppm or less (preferably 1 ppm or less, more preferably 0.1 ppm or less). The processing aid of the present disclosure particularly preferably contains no fluorine (the fluorine content is 0% by mass).

[0166] The water content of the processing aid is preferably 1.0% by mass or less, more preferably 0.5% by mass or less, still more preferably 0.2% by mass or less, and most preferably 0.1% by mass or less. The lower limit is not particularly limited and may be 0% by mass.

[0167] In this specification, the water content is measured by the following method. Measure the mass of the processing aid before and after heating at 130 °C for 24 hours, and calculate according to the following formula. Take the sample three times, calculate each time, then find the average value and adopt the average value. Water content (% by mass) = [(mass of the processing aid before heating (g)) - (mass of the processing aid after heating (g))] / (mass of the processing aid before heating (g)) × 100

[0168] The method for obtaining a processing aid with a water content within the above range is not particularly limited. For example, a material with a low water content may be used to prepare the processing aid under dry conditions, or after preparing the processing aid with ordinary materials and conditions, the water may be removed by heat treatment or the like.

[0169] The processing aid of the present disclosure may be obtained, for example, by performing a mixing step of charging the above lubricant (A) and the above resin (B) into a mixer or the like and mixing them, and a discharging step of discharging the mixture from the mixer or the like. The present disclosure is also a method for manufacturing the above processing aid including the mixing step and the discharging step.

[0170] The method of the above mixing step is not particularly limited, and it may be mixing (kneading) with shear force applied or mixing without shear force applied. Among them, in order to effectively exhibit the above-mentioned moldability, kneading is preferred, and melt kneading is more preferred. In addition, when melt-kneading is performed, each component may be melted in the mixing step, or may be melted before the mixing step.

[0171] In the above manufacturing method, after the discharging step, a molding step of molding the discharged material with a molding machine or the like may be performed. The method of the above molding step is not particularly limited, and examples thereof include extrusion molding, injection molding, blow molding, etc. Among them, in order to effectively exhibit the above molding processability, extrusion molding is preferable.

[0172] For the above extrusion molding, an extruder is used. Examples of the above extruder include a single-screw extruder, a twin-screw extruder, a tandem extruder, etc. The above extruder usually includes a cylinder, a screw accommodated in the cylinder, a die attached to the tip of the cylinder, and a hopper for supplying pellets to the cylinder.

[0173] The various conditions related to the above molding are not particularly limited, and can be appropriately set according to the composition and amount of the composition, the shape and size of the desired molded product, etc.

[0174] The processing aid of the present disclosure is particularly useful as a processing aid for thermoplastic resins (especially polyolefin resins).

[0175] <Masterbatch> The masterbatch of the present disclosure contains the processing aid of the present disclosure and a thermoplastic resin (C). The processing aid of the present disclosure may be added directly to an object such as a thermoplastic resin, or may be in the state of a masterbatch. By adding it in the state of a masterbatch, metering stability and good dispersibility can be obtained.

[0176] Examples of the above-mentioned thermoplastic resin (C) include polyolefin polymers (polyethylene (PE), polypropylene (PP), ethylene-propylene copolymer), polystyrene (PS), AS (acrylonitrile styrene) resin (AS), ABS (acrylonitrile butadiene styrene) resin (ABS), methacrylic resin (PMMA), polymethylpentene (PMP), butadiene resin (BDR), polybutene-1 (PB-1), polyvinyl alcohol (PVA), polyacrylonitrile (PAN), polymethacrylic styrene (MS), ethylene vinyl acetate copolymer (EVA), ethylene-vinyl alcohol copolymer, polyvinyl chloride (PVC), etc. These may be used alone or in combination of two or more. From the viewpoint of better improving the processability, polyolefin polymers (polyolefin resins) are preferred.

[0177] Among the polyolefin polymers, for example, homopolymers (for example, homopolymers of C2-C10 α-olefins, preferably C2-C6 α-olefins) can be mentioned. Specific examples of homopolymers include homopolyethylene and polypropylene (hPP). For example, taking homopolyethylene as an example, such polymers can be produced, for example, by free radical polymerization in a high-pressure process, typically highly branched ethylene homopolymers, often known as LDPE (low-density polyethylene), with a density of less than 0.945 g / cm 3 and often less than 0.935 g / cm 3 and, for example, in the range from 0.900, 0.905, or 0.910 g / cm 3 to 0.920, 0.925, 0.927, 0.930, 0.935, or 0.945 g / cm 3 Unless otherwise specified in this specification, all polymer density values are determined in accordance with ASTM D1505. The sample is molded under ASTM D4703-10a, Procedure C and allowed to stand for 40 hours under ASTM D618-08 (23 ± 2°C and relative humidity 50 ± 10%) before testing.

[0178] In another example, ethylene monomers can be polymerized using known gas, slurry, and / or solution phase polymerization, such as catalysts like chromium-based catalysts, or single-site catalysts like Ziegler-Natta and / or metallocene catalysts, all of which are well-known in the polymerization art and will not be discussed further herein. When more highly linear ethylene homopolymers are produced (e.g., using gas phase or slurry phase polymerization with any of the above catalysts), it is called HDPE (high density polyethylene) and typically has a density in the range of 0.945 to 0.970 g / cm 3 as, for example, above 0.945 g / cm 3 with a density above.

[0179] Furthermore, examples of polymers include copolymers of two or more C2 - C40 α - olefins, such as C2 - C20 α - olefins, such as ethylene - α - olefin copolymers, or propylene - α - olefin copolymers (for example, propylene - ethylene copolymers or propylene - ethylene - diene terpolymers (sometimes known as EPDM or PEDM)). Specific examples contemplated herein include copolymers of ethylene and one or more C3 - C20 α - olefin comonomers (1 - butene, 1 - hexene, 1 - octene, or mixtures of two or more thereof being preferred in various embodiments), such as C4 - C12 α - olefin comonomers. The ethylene copolymer (for example, a copolymer of ethylene and one or more C3 - C20 α - olefins) can contain at least 90, 94, 95, or 96 wt% (for example, in the range from a lower value of 80, 85, 90, 80, 85, 93, 93, 95, 96, or 97 wt% to a higher value of 94, 95, 95.5, 91, 92, 97, 94, 97.5, or 98 wt%), at least 96 wt%, or 96.5 wt% of ethylene - derived units, based on the total amount of ethylene - derived units and comonomer - derived units, and can include a range from any of the lower values to any of the higher values as described above. For example, the ethylene copolymer can contain 94 or 95 mass% to 97 or 98 mass% of ethylene - derived units based on the total amount of ethylene - derived units and comonomer - derived units. The balance of the copolymer (based on ethylene - derived units and comonomer - derived units) consists of comonomer - derived units. For example, comonomer units (for example, units derived from C2 - C20 α - olefins such as units derived from butene, hexene, and / or octene) can be present in the ethylene copolymer in an amount from a lower value of 2, 2.5, 3, 3.5, 4, 4.5, 5, or 6 mass% to a higher value of 3, 4, 5, 6, 7, 8, 9, 10, 15, or 20 mass%, and the range is from the lower value to the intended higher value (provided the higher value is greater than the lower value).

[0180] For ethylene-based, propylene-based, or other alpha-olefin-based copolymers, several suitable comonomers are already known, but in various embodiments, other alpha-olefin comonomers are contemplated. For example, the alpha-olefin comonomer may be linear or branched, and if desired, two or more comonomers can be used. Examples of suitable comonomers include linear C3-C20 alpha-olefins (such as butene, hexene, octene, as already mentioned), and alpha-olefins having one or more C1-C3 alkyl branches or aryl groups. For example, propylene; 3-methyl-1-butene; 3,3-dimethyl-1-butene; 1-pentene; 1-pentene having one or more methyl, ethyl, or propyl substituents; 1-hexene having one or more methyl, ethyl, or propyl substituents; 1-heptene having one or more methyl, ethyl, or propyl substituents; 1-octene having one or more methyl, ethyl, or propyl substituents; 1-nonene having one or more methyl, ethyl, or propyl substituents; ethyl-, methyl- or dimethyl-substituted 1-decene; 1-dodecene; styrene. The above list of comonomers is merely illustrative and is not intended to be limiting. In some embodiments, the comonomer includes propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene and styrene.

[0181] In certain embodiments, the polymer can comprise an ethylene copolymer or, alternatively, can be an ethylene copolymer (according to that described above). The ethylene copolymer can be produced by gas, slurry or solution phase polymerization, and some particularly preferred ethylene copolymers can be produced by gas or slurry phase polymerization. Specific examples are linear low density polyethylene (LLDPE), a copolymer of ethylene and one or more alpha-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 has a density of 0.900, 0.905, 0.907, 0.910 g / cm 3from a low concentration to a density within the range of 0.920, 0.925, 0.930, 0.935, 0.940, or 0.945 g / cm 3 can have a density within the range of high concentration. LLDPE can be distinguished from the above-mentioned LDPE in several respects, many of which are well known in the art, including the degree of branching (which is often negligible if any) in the produced polymer. Note that LLDPE has substantially fewer long-chain branches. In certain embodiments, the polymer of the polymer composition is or comprises metallocene-catalyzed LLDPE (mLLDPE). In still other embodiments, the polymer of the polymer composition is or comprises Ziegler-Natta-catalyzed LLDPE (or ZN-LLDPE).

[0182] Also, in some embodiments, the density of the polymer is in the range of 0.905 to 0.945 g / cm 3 For example, from any of the low values of 0.905, 0.907, 0.908, 0.910, 0.911, 0.912, 0.913, 0.914, or 0.915 g / cm 3 to any of the high values of 0.916, 0.917, 0.918, 0.919, 0.920, 0.924, 0.926, 0.930, 0.935, 0.940, or 0.945 g / cm 3 and the range is from the above-mentioned low value to the high value as intended herein (e.g., 0.910 to 0.925 or 0.935 g / cm 3 , for example 0.912 to 0.925 or 0.915 to 0.918 g / cm 3 ). In still other embodiments, the polymer may be a higher density (e.g., HDPE) having a density in the range of 0.945 g / cm 3 to 0.970 g / cm 3 .

[0183] Furthermore, the rheological properties of the polymer can affect the processing aid composition for molding the molded article. Generally, the processing aid composition is preferably used in a polymer having a melt index (MI or I2, measured at 190°C under a load of 2.16 kg according to ASTM D1238) in the range of 0.1, 0.2, or 0.5 g / 10 min to 1.0, 1.2, 5.0, 10, 2.5, 10, 4.0, or 5.0 g / 10 min, etc., 1.5 g / 2.0 min or less, preferably 2.5 g / 3.0 min or less. The melt index ratio (MIR) (MIR is defined herein as the ratio of the high load melt index (HLMI) (measured according to ASTM D1238 at 190°C under a load of 21.6 kg) to the melt index, or HLMI / MI) can generally have an MIR in the range of 10, 12, or 15 to 19, 20, 21, 22, 25, 27, 30, 35, 40, 45, 50, 60, 65, 70, 75, 80, 85, 90, 95, or 100 in the polymers of some embodiments. Optionally, the MI in such polymers can be less than 1.5 g / 10 min, such as less than 1.0 g / 10 min (for example, from 0.1, 0.2, or 0.5 g / 10 min to 1.0; or any of 1.1, 1.2, 1.3, 1.4, or less than 1.5 g / 10 min).

[0184] Also, the above LLDPE is preferably at least one selected from the group consisting of Ziegler-Natta catalyst type LLDPE and metallocene catalyst type LLDPE. Particularly, metallocene catalyst type LLDPE is preferred.

[0185] The above thermoplastic resin (C) may or may not have crystallinity. When the above thermoplastic resin (C) has crystallinity, those having a melting point of 80 to 300°C are preferred, and those having a melting point of 100 to 200°C are more preferred. The non-crystalline thermoplastic resin (C) preferably has a processing temperature substantially equivalent to that of the crystalline thermoplastic resin (C) with a melting point range indicated.

[0186] In the masterbatch of the present disclosure, the mass ratio of the thermoplastic resin (C) to the processing aid (thermoplastic resin (C): processing aid) is preferably 99:1 to 1:99. The mass ratio is more preferably 97:3 to 50:50, still more preferably 95:5 to 60:40, and particularly preferably 92:8 to 70:30.

[0187] In the masterbatch of the present disclosure, the total content of the thermoplastic resin (C) and the processing aid is preferably 80% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass or more, and particularly preferably 100% by mass.

[0188] The melt flow rate (MFR) of the masterbatch of the present disclosure is preferably 0.1 g / 10 min or more, more preferably 0.5 g / 10 min or more, still more preferably 1 g / 10 min or more, even more preferably 1.5 g / 10 min or more, and preferably 100 g / 10 min or less, more preferably 50 g / 10 min or less, still more preferably 30 g / 10 min or less, even more preferably 20 g / 10 min or less, and particularly preferably 10 g / 10 min or less. Within the above range, the effect of improving processability is better.

[0189] The masterbatch of the present disclosure may contain components other than the thermoplastic resin (C) and the processing aid. Examples of the components other than the thermoplastic resin (C) and the processing aid include anti-blocking agents; ultraviolet absorbers; flame retardants; reinforcing materials such as glass fibers and glass powders; stabilizers such as minerals and flakes; lubricants such as silicone oil and molybdenum disulfide; pigments such as titanium dioxide and valve stems; conductive agents such as carbon black; impact resistance improvers such as rubbers; antioxidants such as hindered phenol-based and phosphorus-based antioxidants; nucleating agents such as metal salts and acetals of sorbitol, anti-blocking agents, and the above-mentioned lubricant (A) can be used.

[0190] The masterbatch of the present disclosure can be obtained, for example, by previously preparing the processing aid of the present disclosure, putting it into a mixer or the like together with the above-mentioned thermoplastic resin (C), and performing a mixing step of mixing, and a discharging step of discharging the mixture from the mixer or the like. It may also be obtained by putting the above-mentioned thermoplastic resin (C), the above-mentioned lubricant (A) and the above-mentioned resin (B) into a mixer or the like and performing a mixing step of mixing and a discharging step of discharging the mixture from the mixer or the like. The present disclosure is also a method for manufacturing the above-mentioned masterbatch including a mixing step and a discharging step.

[0191] In the method for manufacturing the masterbatch of the present disclosure, after the discharging step, a molding step of molding the discharged product with a molding machine or the like may be performed.

[0192] The mixing step, discharging step, and molding step in the method for manufacturing the masterbatch of the present disclosure are the same as those described in the method for manufacturing the processing aid of the present disclosure. The shape of the masterbatch of the present disclosure is not particularly limited and may be powder, granules, pellets, etc., but pellets are preferred because they have excellent handleability and are easy to mold.

[0193] The masterbatch of the present disclosure is particularly useful as a masterbatch for improving the processability of thermoplastic resins (particularly polyolefin resins).

[0194] <Thermoplastic resin composition> The thermoplastic resin composition of the present disclosure includes the processing aid of the present disclosure and / or the masterbatch of the present disclosure, and a thermoplastic resin (D). Thereby, good processability can be obtained. In particular, good extrusion processability can be obtained even during long-run molding. Furthermore, the storage stability of the extruded product is also excellent.

[0195] As the above-mentioned thermoplastic resin (D), the same ones as the above-mentioned thermoplastic resin (C) can be used, and the preferred forms are also the same. The masterbatch of the present disclosure includes the processing aid of the present disclosure and the thermoplastic resin (C). The processing aid of the present disclosure may be added directly to an object such as a thermoplastic resin, or may be added in the state of a masterbatch.

[0196] 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 is preferable to contain the masterbatch of the present disclosure.

[0197] When the thermoplastic resin composition of the present disclosure contains the masterbatch of the present disclosure, the above-mentioned thermoplastic resin (C) and the above-mentioned thermoplastic resin (D) may be of the same type or different types.

[0198] In the thermoplastic resin composition of the present disclosure, the content of the above-mentioned processing aid is preferably 0.001% by mass or more, more preferably 0.02% by mass or more, still more preferably 0.04% by mass or more, and particularly preferably 0.06% by mass or more. Also, it is preferably 3% by mass or less, more preferably 2% by mass or less, still more preferably 1% by mass or less, and particularly preferably 0.6% by mass or less.

[0199] The thermoplastic resin composition of the present disclosure may contain components other than the above-mentioned processing aid, the above-mentioned masterbatch, and the above-mentioned thermoplastic resin (D). Examples of the components other than the above-mentioned processing aid, the above-mentioned masterbatch, and the above-mentioned thermoplastic resin (D) include, for example, an anti-blocking agent; an ultraviolet absorber; a flame retardant; a reinforcing material such as glass fiber and glass powder; a stabilizer such as a mineral and a flake; a lubricant such as silicone oil and molybdenum disulfide; a pigment such as titanium dioxide and a valve handle; a conductive agent such as carbon black; an impact resistance improver such as rubber; an antioxidant such as a hindered phenol type and a phosphorus type; a nucleating agent such as a metal salt and an acetal of sorbitol, an anti-blocking agent, and the above-mentioned lubricant (A) can be used.

[0200] The thermoplastic resin composition of the present disclosure can be obtained, for example, by previously preparing the masterbatch of the present disclosure, putting it into a mixer or the like together with the above thermoplastic resin (D), and performing a mixing step of mixing them, and a discharging step of discharging the mixture from the mixer or the like. It may also be obtained by putting the above thermoplastic resin (D), the above lubricant (A) and the above resin (B), and, if necessary, the above thermoplastic resin (C) into a mixer or the like and performing a mixing step of mixing them, and a discharging step of discharging the mixture from the mixer or the like. The present disclosure is also a method for manufacturing the above thermoplastic resin composition including a mixing step and a discharging step.

[0201] In the method for manufacturing the thermoplastic resin composition of the present disclosure, after the discharging step, a molding step of molding the discharged material with a molding machine or the like may be performed.

[0202] The mixing step, discharging step, and molding step in the method for manufacturing the thermoplastic resin composition of the present disclosure are the same as those described in the method for manufacturing the processing aid of the present disclosure.

[0203] <Molded article> The molded article of the present disclosure is made using the thermoplastic resin composition of the present disclosure, and may be obtained, for example, by performing a molding step of molding the thermoplastic resin composition of the present disclosure. The present disclosure is also a method for manufacturing the molded article of the present disclosure including a molding step. Note that the thermoplastic resin composition of the present disclosure is suitable for a molded article in a tube shape, film shape, or sheet shape, but is also applicable to molded articles of other shapes.

[0204] The above molding step is the same as that described in the method for manufacturing the processing aid of the present disclosure.

[0205] In the above-mentioned molding process, the molding temperature (extrusion temperature) during molding is generally set at a temperature that is equal to or higher than the melting point of the above-mentioned thermoplastic resin (D), lower than the decomposition temperature of the above-mentioned lubricant (A), and lower than the decomposition temperature of the above-mentioned resin (B). When components other than the lubricant (A) and the resin (B) are included, it is preferable to set the molding temperature in consideration of those components. In terms of the significant manifestation of the effect of the above-mentioned processing aid, it is preferably in the range of 160°C or higher and 270°C or lower. In the case of extrusion molding, the above-mentioned molding temperature may also be referred to as the extrusion temperature.

[0206] The use of the molded body of the present disclosure is not particularly limited. For example, it includes bags, coating materials, tableware such as beverage containers, electric wires, cables, pipes, fibers, bottles, gasoline tanks, and other various industrial molded products.

[0207] Although the embodiments have been described above, it will be understood that various changes in form and details can be made without departing from the spirit and scope of the claims.

Examples

[0208] Next, the present disclosure will be described with reference to examples, but the present disclosure is not limited to such examples.

[0209] In the examples and comparative examples, the following materials were used. (Lubricant (A)) Polysorbate60: Polysorbate 60 (MFR: >500 g / 10 min) Zn-St: Zinc stearate (MFR: >500 g / 10 min) Mg-C18(OH): Magnesium 12-hydroxystearate (MFR: >500 g / 10 min) PE-wax #1: General polymerization type polyethylene wax (acid value: 0 mgKOH / g, melting point: 122°C, melt viscosity (140°C): 80 mPa·s, MFR: >500 g / 10 min) PE-wax #2: Metallocene-catalyzed polyethylene wax (acid value: 0 mg KOH / g, melting point: 100 °C, melt viscosity (140 °C): 300 mPa·s, MFR: >500 g / 10 min) PE-wax #3: Acid-modified type polyethylene wax (acid value: 17 mg KOH / g, melting point: 107 °C, melt viscosity (140 °C): 300 mPa·s, MFR: >500 g / 10 min) PE-wax #4: Oxidized type (high acid value) polyethylene wax (acid value: 30 mg KOH / g, melting point: 102 °C, melt viscosity (140 °C): 265 mPa·s, MFR: >500 g / 10 min) (Resin (B1)) EVOH: Ethylene-vinyl alcohol copolymer (ethylene content: 38 mol%, MFR: 1.6 g / 10 min, melting point: 172 °C) PLA: Polylactic acid (MFR: 3 g / 10 min, melting point: 153 °C) PBS: Polybutylene succinate (MFR: 22 g / 10 min, melting point: 114 °C) (Resin (B2)) PLA: Polylactic acid (MFR: 3 g / 10 min, melting point: 153 °C) PBS: Polybutylene succinate (MFR: 22 g / 10 min, melting point: 114 °C) (Matrix resin, carrier resin) m-LLDPE-1: Metallocene-catalyzed linear low-density polyethylene (MFR: 0.7 g / 10 min, melting point: 123 °C, d = 0.926, MIR = 28.1) m-LLDPE-2: Metallocene-catalyzed linear low-density polyethylene (MFR: 2.0 g / 10 min, melting point: 121 °C, d = 0.925, MIR = 23.6) ZN-LLDPE-1: Ziegler-Natta-catalyzed linear low-density polyethylene (MFR: 0.8 g / 10 min, melting point: 123 °C, d = 0.925, MIR = 27.0) ZN-LLDPE-2: Ziegler-Natta-catalyzed linear low-density polyethylene (MFR: 2.0 g / 10 min, melting point: 121 °C, d = 0.918, MIR = 23.2) (Other additive (E) (Synergist)) PCL: Polycaprolactone (Mw: 80,000, melting point: 55 °C) PEG-1: Polyethylene glycol (Mn: 8,000, melting point: 63 °C) MB50-002: Silicone (ultra-high molecular weight silicone-containing masterbatch, manufactured by Dupont) GENIOPLAST PELLET S: Silicone (ultra-high molecular weight silicone, manufactured by Asahi Kasei Wacker) Pebax MV1072: Polyamide-polyether block copolymer (manufactured by Arkema)

[0210] Comparative Examples 1 to 5, Examples 1 to 87 First, the matrix resin (thermoplastic resin (D)), lubricant (A), resin (B1), and resin (B2) were melt-kneaded at a ratio shown in Table 1 using a twin-screw extruder (TEX25αIII manufactured by Japan Steel Works) under the conditions of a cylinder temperature of 180 to 200 °C, a die temperature of 200 °C, and a screw rotation speed of 400 rpm to obtain a compound. Next, the processability of the obtained compound was evaluated by the following extrusion evaluation. The results are shown in Table 1. Since none of the materials of the lubricant (A), resin (B1), and resin (B2) used contained fluorine, the fluorine content in the processing aid was 0% by mass.

[0211] Examples 88 to 90 First, the carrier resin (thermoplastic resin (C)), lubricant (A), resin (B1), and resin (B2) were melt-kneaded at a ratio shown in Table 2 using a twin-screw extruder (TEX25αIII manufactured by Japan Steel Works) under the conditions of a cylinder temperature of 180 to 200 °C, a die temperature of 200 °C, and a screw rotation speed of 400 rpm so that the concentrations of the lubricant (A), resin (B1), and resin (B2) were 25% by mass to obtain a masterbatch (MB). Next, the processability when the obtained masterbatch was dry-blended with the matrix resin at a ratio shown in Table 2 was evaluated by the following extrusion evaluation. The results are shown in Table 2. Since none of the materials of the lubricant (A), resin (B1), and resin (B2) used contained fluorine, the fluorine content in the processing aid was 0% by mass.

[0212] Examples 91 to 95 First, a matrix resin (thermoplastic resin (D)), a lubricant (A), a resin (B1), a resin (B2), and other additives (E) were melt-kneaded at a ratio shown in Table 3 using a twin-screw extruder (TEX25αIII manufactured by Japan Steel Works, Ltd.) under the conditions of a cylinder temperature of 180 to 200°C, a die temperature of 200°C, and a screw rotation speed of 400 rpm to obtain a compound. Next, the processability of the obtained compound was evaluated by the following extrusion evaluation. The results are shown in Table 3. Since none of the materials of the lubricant (A), the resin (B1), and the resin (B2) used contained fluorine, the fluorine content in the processing aid was 0% by mass.

[0213] <Extrusion evaluation> Each material was extruded for 60 minutes using a single-screw extruder (Rheomex OS manufactured by HAAKE, L / D: 33, screw diameter: 20 mm, die diameter: 2 mm) under the conditions of a cylinder temperature of 170 to 200°C, a die temperature of 200°C, and a shear rate of 450 / second, and evaluated by the following items. Before each test run, linear low-density polyethylene containing 15% by mass of silica was charged into the hopper, the screw rotation speed was increased to 150 rpm, and purging was performed for about 15 minutes. Next, the same matrix resin as that used in the test was charged and purged for about 15 minutes, and then the screw rotation speed was returned to 30 rpm and extrusion was performed until the temperature became stable. After confirming that the initial pressure had returned, the next experiment was conducted. If the initial pressure had not returned, the above purging operation was repeated until the initial pressure returned, and then the next experiment was conducted. (Melt fracture (MF) state) Extrusion was performed using only the matrix resin until the pressure became stable in a state where melt fracture occurred over the entire surface. Then, when the screw could be seen thereafter, it was set to zero, and extrusion was performed for 60 minutes. For examples using a processing aid or a masterbatch, these were charged into the hopper at the zero point. Then, the appearance of the strand at the initial stage of extrusion and the strand at the completion of extrusion was visually and palpably confirmed, and the change in MF observed at the initial stage of extrusion was evaluated according to the following criteria. The smaller the value, the better. Disappearance: MF completely disappears Not disappearing: The MF is the same as that in the case of only the matrix resin, or the MF decreases but does not completely disappear. (Die build-up (DBU)) For the sample in which MF completely disappeared, extrusion evaluation was performed by long-run molding (3 hours), the state of the die after extrusion was visually confirmed, and the presence or absence of DBU (die fouling) was evaluated. Evaluation was performed on a 5-point scale from 1 to 5. The smaller the value, the less the amount of DBU generated and the better. 1 indicates that no DBU occurred. (Storage stability test) Regarding Example 5, Example 12, Example 17, Example 22, Example 30, Example 31, and Example 81, strand samples were collected after long-run molding (3 hours) and allowed to stand at 80 °C for 24 hours. After 24 hours, sensory evaluation (tactile sensation) was performed on the slipperiness of the strand surface, and the slipperiness before and after the test was evaluated according to the following criteria (presence or absence of bleed-out). The results are shown in Table 1. Yes: The slipperiness after the test is higher than that before the test. No: No change before and after the test.

[0214] [Table 1]

[0215] [Table 2]

[0216] [Table 3]

[0217] From the results of the examples, it is presumed that the effects of the present invention were obtained by the following mechanism. Since the molten resin (B) has a functional group, the interaction with the metal on the inner surface of the extruder is promoted, and the resin (B) adheres to the metal surface on the inner surface of the extruder to form a coating layer, thereby improving the fluidity of the matrix resin (LLDPE). It is considered that by using the resin (B) and the lubricant (A) in combination, a synergistic effect is exhibited and the processability is remarkably improved.

Claims

1. A processing aid comprising a lubricant (A) and a resin (B), wherein the resin (B) is a processing aid containing a structural unit represented by the following formula 1. -X-(CR １ R ２ ) ｎ -Y-(CR ３ R ４ ) ｍ -Z- (Formula 1) (In formula 1, X is a single bond or a divalent group which may have a functional group, Y and Z are each independently a single bond, -O-, -C(=O)-, -C(=O)O-, -OC(=O)O-, -C(=NR')-, -C(=NR')O-, -OC(=NR')O-, -S-, -S(=O)-, -S(=O)O-, -OS(=O)O-, -S(=O) ２ -, -S(=O) ２ O-, -OS(=O) ２ O-, -P(=O)-, -P(=O)O-, -OP(=O)O-, -P(=O) ２ -, -P(=O) ２ O-, -OP(=O) ２ O-, -NR'-, and -C(OR')R'- (wherein R' is independently, in each occurrence, a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms), and is a group composed of at least one selected from the group consisting of R １ , R ２ , R ３ and R ４ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, n and m are each independently an integer from 0 to 10, at least one of X, Y and Z is —C(═O)—, —C(═O)O—, —OC(═O)O— or —C(OR’)R’—.)

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

3. The processing aid according to claim 1 or 2, wherein the lubricant (A) is at least one selected from the group consisting of waxes, alcohols and surfactants.

4. The processing aid according to claim 1 or 2, wherein the lubricant (A) is at least one selected from the group consisting of sugar-based surfactants, metal soaps and polyethylene waxes.

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

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

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

8. In formula 1, Y and Z are each independently a group composed of at least one selected from the group consisting of a single bond, —O—, —C(═O)—, —C(═O)O—. The processing aid according to claim 7.

9. The processing aid according to claim 1 or 2, wherein the melting point of the resin (B) is 65° C. or higher.

10. The processing aid according to claim 1 or 2, wherein the resin (B) is at least one selected from the group consisting of polylactic acid, polybutylene succinate, ethylene-vinyl alcohol copolymer and polybutylene succinate adipate.

11. The lubricant (A) is at least one selected from the group consisting of polysorbate, zinc stearate, magnesium 12-hydroxystearate and polyethylene wax, The processing aid according to claim 1 or 2, wherein the resin (B) is at least one selected from the group consisting of polylactic acid, polybutylene succinate and ethylene-vinyl alcohol copolymer.

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

13. The masterbatch according to claim 12, wherein the thermoplastic resin (C) is a polyolefin resin.

14. The thermoplastic resin (C) is at least one selected from the group consisting of metallocene-catalyzed linear low-density polyethylene and Ziegler-Natta-catalyzed linear low-density polyethylene, The masterbatch according to claim 12, wherein the mass ratio of the thermoplastic resin (C) to the processing aid (thermoplastic resin (C): processing aid) is 92:8 to 70:

30.

15. A thermoplastic resin composition comprising the processing aid according to claim 1 or 2 and / or the masterbatch according to claim 12 or 13, and a thermoplastic resin (D).

16. The thermoplastic resin composition according to claim 15, wherein the thermoplastic resin (D) is a polyolefin resin.

17. The thermoplastic resin (D) is at least one selected from the group consisting of metallocene-catalyzed linear low-density polyethylene and Ziegler-Natta-catalyzed linear low-density polyethylene, The thermoplastic resin composition according to claim 16, wherein the content of the processing aid is 0.02 to 3% by mass.

18. A molded article using the thermoplastic resin composition according to claim 15.

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

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

21. A method for producing the masterbatch according to claim 12 or 13, comprising a mixing step and an extrusion step.

22. A method for producing the thermoplastic resin composition according to claim 15, comprising a mixing step and an extrusion step.

23. A method for producing the molded article according to claim 18, comprising a molding step.

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