Stabilized rotationally molded polyolefins

Abstract

The present invention provides a process for producing plastic articles stabilized against the harmful effects of heat, light, and oxygen, as well as hollow plastic articles. [Solution] Stability against harmful effects of heat, light, and oxygen is provided to polyolefin hollow articles prepared via a rotational molding process by incorporating therein hindered amine light stabilizers, ultraviolet absorbers, and thioether additives.

Description

[Technical Field]

[0001] This disclosure relates to polyolefin compositions prepared by a rotational molding process having improved mechanical properties. [Background technology]

[0002] Rotational molding (or rotomolding) is a manufacturing process for preparing hollow plastic articles. Generally, plastic material is filled into one side of a mold, and then closed with the other side. The closed mold is heated and rotated around different axes, causing the molten polymer to coat the inside of the mold. This process is called "sintering." The mold is then cooled, and the molded article is removed. This process can require temperatures exceeding approximately 300°C, or even exceeding approximately 400°C.

[0003] Rotational molding processes can be used to prepare items such as storage tanks for water or oil, kayaks, toys, waste containers, and equipment casings. Typically, rotational molding processes use polyolefin substrates, such as polyethylene.

[0004] In rotational molding processes, processing temperatures are typically high and heating times are long. Even during the polymer cooling cycle (crystallization), the parts can be exposed to the harmful effects of heat. Rotationally molded parts are typically cooled slowly to avoid distortion and warping, and depending on the size and thickness of the part, it may be exposed to a considerable amount of heat during the cooling phase. Even after being removed from the mold, plastic parts may still be cooling and crystallizing. Prolonged exposure to heat and oxygen adversely affects the mechanical properties of rotationally molded plastic parts. Current processing stabilization packages do not provide rotationally molded parts with desired mechanical properties, such as impact strength or ductility. [Overview of the Initiative]

[0005] Accordingly, a hollow plastic article stabilized against the harmful effects of heat, light, and oxygen is disclosed, the article comprising a polyolefin substrate, the polyolefin substrate incorporating therein a hindered amine light stabilizer, an ultraviolet absorber, and a thioether additive.

[0006] Also disclosed is a process for producing hollow plastic articles, which includes incorporating a hindered amine light stabilizer, an ultraviolet absorber, and a thioether additive into a polyolefin substrate to provide a fully compounded polyolefin mixture; adding the mixture to a mold; heating the mold to a temperature above 280°C; rotating the mold around at least two axes so that the molten polyolefin mixture coats the inside of the mold; cooling the mold while still rotating; opening the mold; and removing the formed hollow article. [Modes for carrying out the invention]

[0007] In certain embodiments, the polyolefin substrate includes polyethylene. Polyethylene includes, for example, high-density polyethylene (HDPE), high-molecular-weight high-density polyethylene (HMW HDPE), ultra-high-molecular-weight high-density polyethylene (UHMW HDPE), medium-density polyethylene (MDPE), low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), branched low-density polyethylene (BLDPE), or polyethylene and ethylene copolymers prepared using a Phillips catalyst and polyethylene blend. The ethylene copolymer may contain different proportions of comonomers. In some embodiments, the comonomers include 1-olefins such as propene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, or isobutylene; cycloolefins such as styrene, cyclopentene, cyclohexene, or norbornene; or dienes such as butadiene, isoprene, 1,4-hexadiene, cyclopentadiene, dicyclopentadiene, norbornadiene, or ethylidenenorbornene.

[0008] Polyolefin substrates also include polyethylene blends with polyolefins. Examples include mixtures of polyethylene with polypropylene (PP), and mixtures of various PE types, such as mixtures containing two or more high-density polyethylene (HDPE), high molecular weight high-density polyethylene (HMW HDPE), ultra-high molecular weight high-density polyethylene (UHMW HDPE), medium-density polyethylene (MDPE), low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), branched low-density polyethylene (BLDPE), or ethylene-propylene-diene polymer (EPDM) containing a high proportion of dienes. Specific embodiments of polymer mixtures include, for example, three-component mixtures such as PP / HDPE, PP / LLDPE, and LLDPE / HDPE, as well as PP / HDPE / LLDPE. In specific embodiments, the polymers may be linear or branched and may be formulated with or without crosslinking (e.g., chemical crosslinking).

[0009] The polyolefin substrate may incorporate other polymers therein, such as polystyrene, polyamide, polyester, polycarbonate, epoxy resin, polyurethane, copolymers thereof (e.g., random or block copolymers), or mixtures thereof. In some embodiments, such “other” polymers may be present in the finished article in any of the following amounts based on the total weight of the finished article: about 1% by weight, about 2% by weight, about 3% by weight, about 4% by weight, about 5% by weight, about 6% by weight, or about 7% by weight, to about 8% by weight, about 9% by weight, about 10% by weight, about 11% by weight, about 12% by weight, about 13% by weight, about 14% by weight, or about 15% by weight.

[0010] In some embodiments, the hollow article may contain a hindered amine light stabilizer in any amount from about 50 ppm by weight (parts per million), about 100 ppm by weight, about 200 ppm by weight, about 300 ppm by weight, about 400 ppm by weight, about 500 ppm by weight, or about 600 ppm by weight, to about 700 ppm by weight, about 800 ppm by weight, about 900 ppm by weight, about 1000 ppm by weight, about 1100 ppm by weight, about 1200 ppm by weight, about 1300 ppm by weight, about 1400 ppm by weight, about 1500 ppm by weight, about 1600 ppm by weight, about 1700 ppm by weight, about 1800 ppm by weight, about 1900 ppm by weight, or about 2000 ppm by weight, based on the total weight of the article.

[0011] In other embodiments, the hollow article may contain a hindered amine light stabilizer in any of the following amounts based on the total weight of the article: about 0.1% by weight, about 0.2% by weight, about 0.5% by weight, about 1.0% by weight, about 1.5% by weight, about 2.0% by weight, about 2.5% by weight, or about 3.0% by weight, ranging from about 3.5% by weight, about 4.0% by weight, about 4.5% by weight, about 5.0% by weight, about 5.5% by weight, about 6.0% by weight, about 6.5% by weight, about 7.0% by weight, or about 7.5% by weight.

[0012] In some embodiments, the hollow articles may contain an ultraviolet absorber in an amount ranging from about 50 ppm by weight (parts per million), about 100 ppm by weight, about 200 ppm by weight, about 300 ppm by weight, about 400 ppm by weight, about 500 ppm by weight, or about 600 ppm by weight, to about 700 ppm by weight, about 800 ppm by weight, about 900 ppm by weight, about 1000 ppm by weight, about 1100 ppm by weight, about 1200 ppm by weight, about 1300 ppm by weight, about 1400 ppm by weight, about 1500 ppm by weight, about 1600 ppm by weight, about 1700 ppm by weight, about 1800 ppm by weight, about 1900 ppm by weight, or about 2000 ppm by weight, based on the total weight of the article.

[0013] In other embodiments, the hollow article may contain an ultraviolet absorber in any of the following amounts based on the total weight of the article: about 0.1% by weight, about 0.2% by weight, about 0.5% by weight, about 1.0% by weight, about 1.5% by weight, about 2.0% by weight, about 2.5% by weight, or about 3.0% by weight, ranging from about 3.5% by weight, about 4.0% by weight, about 4.5% by weight, about 5.0% by weight, about 5.5% by weight, about 6.0% by weight, about 6.5% by weight, about 7.0% by weight, or about 7.5% by weight.

[0014] In some embodiments, the hollow article may contain a thioether additive in any amount from about 50 ppm by weight (parts per million), about 100 ppm by weight, about 200 ppm by weight, about 300 ppm by weight, about 400 ppm by weight, about 500 ppm by weight, or about 600 ppm by weight, to about 700 ppm by weight, about 800 ppm by weight, about 900 ppm by weight, about 1000 ppm by weight, about 1100 ppm by weight, about 1200 ppm by weight, about 1300 ppm by weight, about 1400 ppm by weight, about 1500 ppm by weight, about 1600 ppm by weight, about 1700 ppm by weight, about 1800 ppm by weight, about 1900 ppm by weight, or about 2000 ppm by weight, based on the total weight of the article.

[0015] In other embodiments, the hollow article may contain a thioether additive in any of the following amounts based on the total weight of the article: about 0.1% by weight, about 0.2% by weight, about 0.5% by weight, about 1.0% by weight, about 1.5% by weight, about 2.0% by weight, about 2.5% by weight, or about 3.0% by weight, ranging from about 3.5% by weight, about 4.0% by weight, about 4.5% by weight, about 5.0% by weight, about 5.5% by weight, about 6.0% by weight, about 6.5% by weight, about 7.0% by weight, or about 7.5% by weight.

[0016] In certain embodiments, the weight / weight ratio of the hindered amine light stabilizer to the thioether additive is one of approximately 7 / 1, approximately 6 / 1, approximately 5 / 1, or approximately 4 / 1, to one of approximately 3 / 1, approximately 2 / 1, or approximately 1 / 1.

[0017] In some embodiments, the weight / weight ratio of the UV absorber to the thioether additive is from any of about 3 / 1, about 2 / 1, about 1.5 / 1, or about 1 / 1 to any of about 1 / 1.5, about 1 / 2, or about 1 / 3.

[0018] In some embodiments, the hollow article comprises a polyolefin substrate from any of about 50 wt%, about 55 wt%, about 60 wt%, about 65 wt%, about 70 wt%, about 73 wt%, about 76 wt%, about 79 wt%, or about 82 wt% to any of about 85 wt%, about 88 wt%, about 90 wt%, about 93 wt%, or about 95 wt% based on the total weight of the article.

[0019] Hindered amine light stabilizers (HALS) are disclosed, for example, in US2015 / 0284535 and US Pat. Nos. 5,004,770; 5,204,473; 5,096,950; 5,300,544; 5,112,890; 5,124,378; 5,145,893; 5,216,156; 5,844,026; 5,980,783; 6,046,304; 6,117,995; 6,271,377; 6,297,299; 6,392,041; 6,376,584; and 6,472,456.

[0020] Hindered amine light stabilizers include, for example, (1) 1-cyclohexyloxy-2,2,6,6-tetramethyl-4-octadecylaminopiperidine, (2) bis(2,2,6,6-tetramethylpiperidin-4-yl) sebacate, (3) bis(1-acetoxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate, (4) bis(1,2,2,6,6-pentamethylpiperidin-4-yl) sebacate, (5) bis(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate, (6) Bis(1-octyloxy-2,2,6,6-tetramethylpiperidine-4-yl) sebacate, (7) Bis(1-acyl-2,2,6,6-tetramethylpiperidine-4-yl) sebacate, (8) Bis(1,2,2,6,6-pentamethyl-4-piperidyl)n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate, (9) 2,4-Bis[(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidine-4-yl)butylamino]-6-(2-hydroxyethyl Amino-S-triazine, (10) Bis(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidine-4-yl) adipate, (11) 2,4-bis[(1-cyclohexyloxy-2,2,6,6-piperidine-4-yl)butylamino]-6-chloro-s-triazine, (12) 1-(2-hydroxy-2-methylpropoxy)-4-hydroxy-2,2,6,6-tetramethylpiperidine, (13) 1-(2-hydroxy-2-methylpropoxy)-4-oxo-2,2,6,6-tetramethylpiperidine, (14) 1-(2-hydroxy-2-methylpropoxy)-4-octadecanoyloxy-2,2,6,6-tetramethylpiperidine, (15) Bis(1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidine-4-yl) sebacate, (16) Bis(1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidine-4-yl) adipate, (17) 2,4-bis{N-[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidine-4-yl]-N-butylamino}- 6-(2-hydroxyethylamino)-s-triazine, (18) 4-benzoyl-2,2,6,6-tetramethylpiperidine, (19) Di-(1,2,2,6,6-pentamethylpiperidine-4-yl) p-methoxybenzylidenemalonate, (20) 2,2,6,6-tetramethylpiperidine-4-yloctadecanoate, (21) Bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl) succinate, (22) 1,2,2,6,6-pentamethyl-4-aminopiperidine, (23) 2-undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxo-spiro[4,5]decane, (24) Tris(2,2,6,6-tetramethyl-4-piperidyl)nitrilotriacetate, (25) Tris(2-hydroxy-3-(amino-(2,2,6,6-tetramethylpiperidine-4-yl)propyl)nitrilotriacetate, (26) Tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butane-tetracarboxylate, (27) Tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)-1,2,3,4-butane-tetracarboxylate, (28) 1,1'-(1,2-ethanediyl)-bis(3,3,5,5-tetramethylpiperazinone), (29) 3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione, (30) 8-Acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione, (31) 3-dodecyl-1-(2,2,6,6-tetramethyl-4-piperidyl)pyrroridine-2,5-dione, (32) 3-dodecyl-1-(1,2,2,6,6-pentamethyl-4-piperidyl)pyrroridine-2,5-dione, (33) N,N'-bis-formyl-N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine, (33a) Bis(1-undecanyloxy-2,2,6,6-tetramethylpiperidine-4-yl) carbonate, (34) 2,4-bis[(1-cyclohexyloxy-2,2,6,6-piperidine-4-yl)butylamino]-6-chloro-s- Reaction product of triazine and N,N'-bis(3-aminopropyl)ethylenediamine, (35) 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succin Acid condensates, (36) N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)-hexamethylenediamine and 4-tert- Condensate of octylamino-2,6-dichloro-1,3,5-triazine, (37) N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)-hexamethylenediamine and 4- Condensate of cyclohexylamino-2,6-dichloro-1,3,5-triazine, (38) N,N'-bis-(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and 4- Condensate of morpholino-2,6-dichloro-1,3,5-triazine, (39) N,N'-bis-(1,2,2,6,6-pentamethyl-4-piperidyl)hexamethylenediamine and 4- Condensate of morpholino-2,6-dichloro-1,3,5-triazine, (40) 2-Chloro-4,6-bis(4-n-butylamino-2,2,6,6-tetramethylpiperidyl)-1,3,5-triazine and condensates of 1,2-bis(3-aminopropylamino)ethane, (41) 2-Chloro-4,6-di-(4-n-butylamino-1,2,2,6,6-pentamethylpiperidyl)-1,3,5- Condensate of triazine and 1,2-bis-(3-aminopropylamino)ethane, (42) 7,7,9,9-Tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospirol [4,5] Reaction products of decane and epichlorohydrin, (43) Poly[methyl,(3-oxy-(2,2,6,6-tetramethylpiperidine-4-yl)propyl)]siloxane, CAS#182635-99-0, (44) Maleic anhydride-C 18 -C 22 -α-olefin copolymer and 2,2,6,6- Reaction product with tetramethyl-4-aminopiperidine, (45) Oligomer condensates of 2,4-dichloro-6-[(2,2,6,6-tetramethylpiperidine-4-yl)butylamino]-s-triazine, end-capped with 4,4'-hexamethylenebis(amino-2,2,6,6-tetramethylpiperidine) and 2-chloro-4,6-bis(dibutylamino)-s-triazine, (46) 4,4'-Hexamethylenebis(amino-1,2,2,6,6-pentamethylpiperidine) and oligomeric condensates of 2,4-dichloro-6-[(1,2,2,6,6-pentamethylpiperidine-4-yl)butylamino]-s-triazine, end-capped with 2-chloro-4,6-bis(dibutylamino)-s-triazine. (47) 4,4'-Hexamethylenebis(amino-1-propoxy-2,2,6,6-tetramethyl 2,4-dichloro-6-[(1-propoxy-2,2,6,6-tetramethylpiperidine-4-yl)butylamino]-s- (end-capped with piperidine) and 2-chloro-4,6-bis(dibutylamino)-s-triazine Triazine oligomeric condensates, (48) 4,4'-Hexamethylenebis(amino-1-acyloxy-2,2,6,6-tetramethyl 2,4-dichloro-6-[(1-acyloxy-2,2,6,6-tetramethylpiperidine-4-yl)butylamino]-s- (end-capped with piperidine) and 2-chloro-4,6-bis(dibutylamino)-s-triazine Triazine oligomeric condensates, and (49) A product obtained by reacting (a) with (b), where (a) is a product obtained by reacting 1,2-bis(3-aminopropylamino)ethane with cyanuric acid chloride, (b) is (2,2,6,6-tetramethyl The product contains piperidine-4-yl)butylamine.

[0021] The list also includes sterically hindered NH, N-methyl, N-hydroxy, and N-acyloxy analogs of any of the above compounds. For example, to replace an NH-hindered amine with an N-methylhindered amine, an N-methyl analog can be used instead of the NH.

[0022] For illustrative purposes, a portion of the structure of the above compound is shown below. [ka] [ka] [ka] [ka] [ka] [ka]

[0023] In some embodiments, the hindered amine light stabilizer is (2) Bis(2,2,6,6-tetramethylpiperidine-4-yl) sebacate, (20) 2,2,6,6-tetramethylpiperidine-4-yloctadecanoate, (14) 1-(2-hydroxy-2-methylpropoxy)-4-octadecanoyloxy-2,2,6,6-tetramethylpiperidine, (33) N,N'-bis-formyl-N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine, (36) N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)-hexamethylenediamine and 4-tert- Condensate of octylamino-2,6-dichloro-1,3,5-triazine, (38) N,N'-bis-(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and 4- Condensate of morpholino-2,6-dichloro-1,3,5-triazine, (39) N,N'-bis-(1,2,2,6,6-pentamethyl-4-piperidyl)hexamethylenediamine and 4- Condensate of morpholino-2,6-dichloro-1,3,5-triazine, (44) Maleic anhydride-C 18 -C 22 -α-olefin copolymer and 2,2,6,6- Reaction product with tetramethyl-4-aminopiperidine, (45) 4,4'-Hexamethylenebis(amino-2,2,6,6-tetramethyl Oligomer compound condensates of 2,4-dichloro-6-[(2,2,6,6-tetramethylpiperidine-4-yl)butylamino]-s-triazine, end-capped with piperidine and 2-chloro-4,6-bis(dibutylamino)-s-triazine, (47) 4,4'-Hexamethylenebis(amino-1-propoxy-2,2,6,6- 2,4-dichloro-6-[(1-propoxy-2,2,6,6-tetramethylpiperidine-4-) and 2-chloro-4,6-bis(dibutylamino)-s-triazine are end-capped. Oligomer compound condensates of butylamino(I)-s-triazine, and The group can be selected from combinations of these two or three components.

[0024] Certain two- or three-component combinations of hindered amine light stabilizers may be advantageous. For example, two- or three-component combinations may be: (2) Bis(2,2,6,6-tetramethylpiperidine-4-yl) sebacate and (36) N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)-hexamethylenediamine and 4-tert- Condensate of octylamino-2,6-dichloro-1,3,5-triazine; (2) Bis(2,2,6,6-tetramethylpiperidine-4-yl) sebacate and (45) 4,4'-hexamethylenebis(amino-2,2,6,6-tetramethyl Oligomer compound condensates of 2,4-dichloro-6-[(2,2,6,6-tetramethylpiperidine-4-yl)butylamino]-s-triazine, end-capped with piperidine and 2-chloro-4,6-bis(dibutylamino)-s-triazine; (20) 2,2,6,6-tetramethylpiperidine-4-yloctadecanoate and (45) 4,4'-Hexamethylenebis(amino-2,2,6,6-tetramethylpiperidine) and Oligomer condensates of 2,4-dichloro-6-[(2,2,6,6-tetramethylpiperidine-4-yl)butylamino]-s-triazine, end-capped with 2-chloro-4,6-bis(dibutylamino)-s-triazine; (2) Bis(2,2,6,6-tetramethylpiperidine-4-yl) sebacate and (20) 2,2,6,6-tetramethylpiperidine-4-yloctadecanoate; or (2) Bis(2,2,6,6-tetramethylpiperidine-4-yl) sebacate, (14) 1-(2-hydroxy-2-methylpropoxy)-4-octadecanoyloxy-2,2,6,6-tetramethylpiperidine, and (36) N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)-hexamethylenediamine and 4-tert- It is a condensate of octylamino-2,6-dichloro-1,3,5-triazine.

[0025] In some embodiments, HALS(38) or (39) may be replaced with HALS(36) in a combination of two or three components.

[0026] Many of these hindered amine stabilizers are commercially available, such as TINUVIN 770, CHIMASSORB 944, CHIMASSORB 2020, CYASORB UV 3853, CYASORB UV 3529, TINUVIN NOR 371, UVINUL 4050, and UVINUL 5050.

[0027] For two-component HALS combinations, the weight / weight ratio is one of the following: approximately 1 / 19, 1 / 18, 1 / 17, 1 / 16, 1 / 15, 1 / 14, 1 / 13, 1 / 12, 1 / 11, 1 / 10, 1 / 9, 1 / 8, 1 / 7, 1 / 6, 1 / 5, 1 / 4, 1 / 3, 1 / 2, or 1 / 1, or 1 / 2, 1 / 3, 1 / 4, 1 / 5, 1 / 6, 1 / 7, 1 / 8, 1 / 9, 1 / 10, 1 / 11, 1 / 12, 1 / 13, 1 / 14, 1 / 15, 1 / 16, 1 / 17, 1 / 18, 1 / 19, or 1 / 20.

[0028] In a three-component HALS combination, the weight / weight ratio of any two HALS is the same as in a two-component combination.

[0029] In some embodiments, a combination of low-molecular-weight and high-molecular-weight HALS may be used. The low-molecular-weight stabilizer has a molecular weight of about 200 g / mol to about 1000 g / mol. The high-molecular-weight stabilizer has a molecular weight of about 1200 g / mol to about 10,000 g / mol.

[0030] Some low molecular weight hindered amines are (1) to (33a). Some high molecular weight hindered amines are (34) to (49). For oligomeric or polymeric hindered amines, the repeating unit "n" is a value such that the average molecular weight is approximately 1200 g / mol to approximately 10,000 g / mol.

[0031] Ultraviolet (UV) absorbers may be selected from the group consisting of oxamide, hydroxyphenylbenzotriazole, tris-aryl-s-triazine, hydroxybenzoate, 2-hydroxybenzophenone, and cyanoacrylate ultraviolet light absorbers (UVA).

[0032] Oxamide UVA includes, for example, 4,4′-dioctyloxyoxanilide, 2,2′-diethoxyoxanilide, 2,2′-dioctyloxy-5,5′-di-tert-butoxanilide, 2,2′-didodecyloxy-5,5′-di-tert-butoxanilide, 2-ethoxy-2′-ethyloxanilide (N'-(2-ethoxyphenyl)-N-(2-ethylphenyl)oxamide), N,N′-bis(3-dimethylaminopropyl)oxamide, 2-ethoxy-5-tert-butyl-2′-ethoxanilide and mixtures thereof with 2-ethoxy-2′-ethyl-5,4′-di-tert-butoxanilide, mixtures of o- and p-methoxy-disubstituted oxanilides, and mixtures of o- and p-ethoxy-disubstituted oxanilides.

[0033] Hydroxyphenylbenzotriazole UVA is, for example, U.S. Patent Nos. 3,004,896, 3,055,896, 3,072,585, 3,074,910, 3,189,615, 3,218,332, 3,230,194, 4,127,586, 4,226,763, 4,275,004, 4,278,589, 4,315,848, and 4,347. ,180, No. 4,383,863, No. 4,675,352, No. 4,681,905, No. 4,853,471, No. 5,268,450, No. 5,278,314, No. 5,280,124 , No. 5,319,091, No. 5,410,071, No. 5,436,349, No. 5,516,914, No. 5,554,760, No. 5,563,242, No. 5,574,166, No. 5,6 These are disclosed in Patent Nos. 07,987, 5,977,219, and 6,166,218, for example, 2-(2-hydroxy-5-methylphenyl)-2H-benzotriazole, 2-(3,5-di-t-butyl-2-hydroxyphenyl)-2H-benzotriazole, 2-(2-hydroxy-5-t-butylphenyl)-2H-benzotriazole, and 2-(2-hydroxy-5-t-octylphenyl)-2H-benzo Triazole, 5-chloro-2-(3,5-di-t-butyl-2-hydroxyphenyl)-2H-benzotriazole, 5-chloro-2-(3-t-butyl-2-hydroxy-5-methylphenyl)-2H-benzotriazole, 2-(3-sec-butyl-5-t-butyl-2-hydroxyphenyl)-2H-benzotriazole, 2-(2-hydroxy-4-octyloxyphenyl)-2H-benzotriazole, 2-(3,5-di-t-amyl-2-hydroxyphenyl)-2H-benzotriazole, 2-(3,5-bis-α-cumyl-2-hydroxyphenyl)-2H-benzotriazole, 2-(3-t-butyl-2-hydroxy-5-(2-(ω-hydroxy-octa-(ethyleneoxy)carbonyl-ethyl)-,phenyl)-2H-benzotriazole, 2-(3-dodecyl-2-hydroxy-5-methylphenyl)-2H-benzotriazole, 2-(3-t-butyl-2-hydroxy-5-(2-O (Cutyloxycarbonyl)ethylphenyl)-2H-benzotriazole, dodecylated 2-(2-hydroxy-5-methylphenyl)-2H-benzotriazole, 2-(3-t-butyl-2-hydroxy-5-(2-octyloxycarbonylethyl)phenyl)-5-chloro-2H-benzotriazole, 2-(3-tert-butyl-5-(2-(2-ethylhexyloxy)-carbonylethyl)-2-hydroxyphenyl)-5-chloro-2H-benzotriazole, 2-(3-t-butyl Tyl-2-hydroxy-5-(2-methoxycarbonylethyl)phenyl)-5-chloro-2H-benzotriazole, 2-(3-t-butyl-2-hydroxy-5-(2-methoxycarbonylethyl)phenyl)-2H-benzotriazole, 2-(3-t-butyl-5-(2-(2-ethylhexyloxy)carbonylethyl)-2-hydroxyphenyl)-2H-benzotriazole, 2-(3-t-butyl-2-hydroxy-5-(2-isooctyloxycarbonylethyl)phenyl -2H-benzotriazole, 2,2'-methylene-bis(4-t-octyl-(6-2H-benzotriazole-2-yl)phenol), 2-(2-hydroxy-3-α-cumyl-5-t-octylphenyl)-2H-benzotriazole, 2-(2-hydroxy-3-t-octyl-5-α-cumylphenyl)-2H-benzotriazole, 5-fluoro-2-(2-hydroxy-3,5-di-α-cumylphenyl)-2H-benzotriazole, 5-chloro-2-(2-hydroxy-3,5-di-α-cumylphenyl)-2H-benzotriazole, 5-chloro-2-(2-hydroxy-3-α-cumyl-5-t-octylphenyl)-2H-benzotriazole, 2-(3-t-butyl-2-hydroxy-5-(2-isooctyloxycarbonylethyl)phenyl)-5-chloro-2H-benzotriazole, 5-trifluoromethyl-2-(2-hydroxy-3-α-cumyl-5-t-octylphenyl)-2H-benzotriazole, 5-trifluoromethyl-2-(2-hydroxy-5-t-octylphenyl)-2H-benzotriazole, 5-trifluoromethyl-2-(2-hydroxy-3,5-di-t-octylphenyl)-2H-benzotriazole, methyl3-(5-trifluoromethyl-2H-benzotriazole-2-yl)-5-t- These are 4-hydroxyhydrocinnamate, 5-butylsulfonyl-2-(2-hydroxy-3-α-cumyl-5-t-octylphenyl)-2H-benzotriazole, 5-trifluoromethyl-2-(2-hydroxy-3-α-cumyl-5-t-butylphenyl)-2H-benzotriazole, 5-trifluoromethyl-2-(2-hydroxy-3,5-di-t-butylphenyl)-2H-benzotriazole, 5-trifluoromethyl-2-(2-hydroxy-3,5-di-α-cumylphenyl)-2H-benzotriazole, 5-butylsulfonyl-2-(2-hydroxy-3,5-di-t-butylphenyl)-2H-benzotriazole, and 5-phenylsulfonyl-2-(2-hydroxy-3,5-di-t-butylphenyl)-2H-benzotriazole.

[0034] Tris-aryl-s-triazine UVA is, for example, U.S. Patent Nos. 3,843,371, 4,619,956, 4,740,542, 5,096,489, 5,106,891, 5,298,067, 5,300,414, 5,354,794, 5,461,151, 5,476,937, 5,489,503, 5,543,518, 5,556,973, 5,597,854, 5,681,955, 5,726,309, and 5,736,597. These are disclosed in Patent Nos. 5,942,626, 5,959,008, 5,998,116, 6,013,704, 6,060,543, 6,242,598, and 6,255,483, for example, 4,6-bis-(2,4-dimethylphenyl)-2-(2-hydroxy-4-octyloxyphenyl)-s-triazine, CYASORB1164, 4,6-bis-(2,4-dimethylphenyl)-2-(2,4-dihydroxyphenyl)-s-triazine, 2,4-bis(2,4-dihydroxyphenyl) -6-(4-chlorophenyl)-s-triazine, 2,4-bis[2-hydroxy-4-(2-hydroxyethoxy)phenyl]-6-(4-chlorophenyl)-s-triazine, 2,4-bis[2-hydroxy-4-(2-hydroxy-4-(2-hydroxyethoxy)phenyl]-6-(2,4-dimethylphenyl)-s-triazine, 2,4-bis[2-hydroxy-4-(2-hydroxyethoxy)phenyl]-6-(4-bromophenyl)-s-triazine, 2,4-bis[2-hydroxy-4-(2-acetoxyethoxy)phenyl]-6-( 4-chlorophenyl)-s-triazine, 2,4-bis(2,4-dihydroxyphenyl)-6-(2,4-dimethylphenyl)-s-triazine, 2,4-bis(4-biphenylyl)-6-(2-hydroxy-4-octyloxycarbonylethylideneoxyphenyl)-s-triazine, 2-phenyl-4-[2-hydroxy-4-(3-sec-butyloxy-2-hydroxypropyloxy)phenyl]-6-[2-hydroxy-4-(3-sec-amyloxy-2-hydroxypropyloxy)phenyl]-s-triazine, 2,4-bis(2,4-dimethylphenyl)-6-[2-hydroxy-4-(3-benzyloxy-2-hydroxypropyloxy)phenyl]-s-triazine, 2,4-bis(2-hydroxy-4-n-butyloxyphenyl)-6-(2,4-di-n-butyloxyphenyl)-s-triazine, 2,4-bis(2,4-dimethylphenyl)-6-[2-hydroxy-4-(3-nonyloxy*-2-hydroxypropyloxy)-5-α-cumylphenyl]-s-triazine (* is octyloxy, nonyloxy, and deci) (Shows a mixture of hydroxyl groups), methylenebis-{2,4-bis(2,4-dimethylphenyl)-6-[2-hydroxy-4-(3-butyloxy-2-hydroxypropoxy)phenyl]-s-triazine}, a mixture of methylene crosslinked dimers crosslinked at the 3:5', 5:5', and 3:3' positions in a 5:4:1 ratio, 2,4,6-tris(2-hydroxy-4-isooctyloxycarbonylisopropylideneoxyphenyl)-s-triazine, 2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy- 4-Hexyloxy-5-α-Cumylphenyl)-s-triazine, 2-(2,4,6-trimethylphenyl)-4,6-bis[2-hydroxy-4-(3-butyloxy-2-hydroxypropyloxy)phenyl]-s-triazine, 2,4,6-Tris[2-hydroxy-4-(3-sec-butyloxy-2-hydroxypropyloxy)phenyl]-s-triazine, 4,6-bis-(2,4-dimethylphenyl)-2-(2-hydroxy-4-(3-dodecyloxy-2-hydroxypropoxy)-phenyl A mixture of 4,6-bis-(2,4-dimethylphenyl)-2-(2-hydroxy-4-(3-tridecyloxy-2-hydroxypropoxy)-phenyl)-s-triazine, TINUVIN400, 4,6-bis-(2,4-dimethylphenyl)-2-(2-hydroxy-4-(3-(2-ethylhexyloxy)-2-hydroxypropoxy)-phenyl)-s-triazine, and 4,6-diphenyl-2-(4-hexyloxy-2-hydroxyphenyl)-s-triazine.

[0035] Hydroxybenzoate UV absorbers include, for example, esters of substituted and unsubstituted benzoic acid, such as 4-tert-butylphenylsalicylic acid, phenylsalicylic acid, octylphenylsalicylic acid, dibenzoylresorcinol, bis(4-tert-butylbenzoyl)resorcinol, benzoylresorcinol, 2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, and 2-methyl-4,6-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate.

[0036] Examples of 2-hydroxybenzophenone UV absorbers include 4-hydroxy, 4-methoxy, 4-octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2',4'-trihydroxy, and 2'-hydroxy-4,4'-dimethoxy derivatives.

[0037] Examples of cyanoacrylate UV absorbers include pentaerythritol tetrakis(2-cyano-3,3-diphenylacrylate), α-cyano-β,β-diphenylacrylate ethyl ester or isooctyl ester, and α-cyano-β-methyl-p-methoxycinnamate methyl ester or butyl ester.

[0038] Many UVA filters are commercially available, such as TINUVIN326, TINUVIN234, TINUVIN1577, TINUVIN1600, CYASORB UV1164, CYASORB THT, CYASORB UV2908, CHIMASSORB81, and UVINUL3030.

[0039] Thioether additives include, for example, mercaptan-containing compounds or disulfide-containing compounds. In some embodiments, the mercaptan-containing compound is of formula [ka] It contains one or more parts, for example, 1, 2, 3, or 4 parts.

[0040] In some embodiments, the mercaptan-containing compound is of the formula [ka] It contains one or more of the following parts, for example, 1, 2, 3, or 4 parts, where R is a hydrocarbyl group.

[0041] For example, in some embodiments, the thioether additive is given by formula . [ka] The compound contains the following, where each R is independently a hydrocarbyl group.

[0042] The disulfide-containing compound is of the formula RSSR, where each R is independently a hydrocarbyl group.

[0043] The phrase "Each R is independently a hydrocarbyl group" means that each R may be the same as or different from any other R group.

[0044] In some embodiments, the thioether additive includes dilauryl thiodipropionate, distearyl thiodipropionate, pentaerythritol tetrakis(β-lauryl thiopropionate), distearyl disulfide, or dilauryl disulfide.

[0045] In some embodiments, the hydrocarbyl group is C2-C 40 Hydrocarbyl group, C2-C 24It may be a hydrocarbyl group or a C2-C5 hydrocarbyl group. The hydrocarbyl is a linear or branched alkyl or alkenyl that can be interrupted or substituted by any hydrocarbon-containing group, for example, one or more heteroatom-containing groups or aryl groups, e.g., interrupted by one or more -O-, -NH-, or -C(O)O- groups and / or substituted with one or more hydroxyl, carboxyl, amino, thiol, phosphonate, or aryl groups. The aryl group includes phenyl.

[0046] In some embodiments, the hydrocarbyl may be nonyl, decyl, undecyl, 1-methylundecyl, lauryl(dodecyl), tridecyl, or stearyl(octadecyl).

[0047] Alkyls may be linear or branched and may include methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, 2-ethylbutyl, n-pentyl, isopentyl, 1-methylpentyl, 1,3-dimethylbutyl, n-hexyl, 1-methylhexyl, n-heptyl, isoheptyl, 1,1,3,3-tetramethylbutyl, 1-methylheptyl, 3-methylheptyl, n-octyl, tert-octyl, 2-ethylhexyl, 1,1,3-trimethylhexyl, 1,1,3,3-tetramethylpentyl, nonyl, decyl, undecyl, 1-methylundecyl, dodecyl, and octadecyl. Alkenyls are alkyls containing an ethylenically unsaturated group.

[0048] In some embodiments, one or more additional additives may be incorporated into the hollow article of the present invention. Further additives may be selected from the group consisting of antioxidants and acid scavengers.

[0049] The antioxidant may be selected from the group consisting of hindered phenol antioxidants, organophosphate stabilizers, dialkylhydroxylamine stabilizers, amine oxide stabilizers, and tocopherols. In some embodiments, the antioxidant includes a combination of an organophosphate stabilizer and a hindered phenol antioxidant, a dialkylhydroxylamine stabilizer, a combination of an organophosphate stabilizer and a dialkylhydroxylamine stabilizer, an amine oxide stabilizer, or a combination of an organophosphate stabilizer and an amine oxide stabilizer.

[0050] Furthermore, antioxidants also include vitamin E and vitamin E acetate (tocopherol). Each can be used individually, in combination with each other, or in combination with one or more antioxidants selected from the group consisting of hindered phenol antioxidants, dialkylhydroxylamine stabilizers, organophosphate stabilizers, and amine oxide stabilizers.

[0051] Organophosphate stabilizers include, for example, known phosphite and phosphonite stabilizers, such as triphenyl phosphite, diphenylalkyl phosphite, phenyl dialkyl phosphite, tris(nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearyl pentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl) phosphite, bis(2,4-di-α-cumylphenyl)pentaerythritol diphosphite, diisodecyl pentaerythritol diphosphite, and bis(2 ,4-di-tert-butylphenyl) pentaerythritol diphosphite (D), bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite (E), bisisodecyloxy-pentaerythritol diphosphite, bis(2,4-di-tert-butyl-6-methylphenyl) pentaerythritol diphosphite, bis(2,4,6-tri-tert-butylphenyl) pentaerythritol diphosphite, tristearyl sorbitol triphosphite, tetrakis(2,4-di-tert-butylphenyl) (Nyl)4,4'-biphenylene-diphosphonite (H), 6-isooctyloxy-2,4,8,10-tetra-tert-butyl-dibenzo[d,f][1,3,2]dioxaphosphine (C), 6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-dibenzo[d,g][1,3,2]dioxaphosphosine (A), bis(2,4-di-tert-butyl-6-methylphenyl)methylphosphite, bis(2,4-di-tert-butyl-6-methylphenyl)ethylphosphite (G), 2,2',2''-nitrilo[tri Ethyl tris(3,3'5,5'-tetra-tert-butyl-1,1'-biphenyl-2,2'-diyl) phosphite](B), bis(2,4-di-t-butylphenyl) octyl phosphite, poly(4,4'-{2,2'-dimethyl-5,5'-di-t-butylphenyl sulfide-}octyl phosphite), poly(4,4'-{-isopropylidenediphenol}-octyl phosphite), poly(4,4'-{isopropylidenebis[2,6-dibromophenol]}-octyl phosphite), poly(4,4'-{2,2'-dimethyl-5,5'-di-t-butylphenyl sulfide}-pentaerythrityl diphosphite), [ka] [ka] It includes.

[0052] Suitable organophosphate stabilizers are also liquid stabilizers, such as those disclosed in U.S. Patent Application Publication No. 2010 / 048782 and U.S. Patent No. 7,888,414, including liquid phosphates P-2, P-3, and P-4. Suitable liquid organophosphate stabilizers are also disclosed in U.S. Patent Application Publication Nos. 2013 / 0225736 and 2010 / 0029844, and U.S. Patent Nos. 7,468,410 and 8,304,477.

[0053] Hindered phenol antioxidants include, for example, tris(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris-(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, the calcium salt of the monoethyl ester of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], or octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate.

[0054] The combination of an organophosphate stabilizer and a hindered phenol antioxidant may be tris(2,4-di-tert-butylphenyl) phosphite and pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] or octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate.

[0055] The weight / weight ratio of the organic phosphorus stabilizer to the hindered phenolic antioxidant can be any of about 9 / 1, about 8 / 1, about 7 / 1, about 6 / 1, about 5 / 1, about 4 / 1, 3 / 1, about 2 / 1, or about 1 / 1 to any of about 1 / 2, about 1 / 3, about 1 / 4, about 1 / 5, about 1 / 6, about 1 / 7, about 1 / 8, or about 1 / 9.

[0056] The hydroxylamine stabilizer is, for example, N,N-dibenzylhydroxylamine, N,N-diethylhydroxylamine, N,N-dioctylhydroxylamine, N,N-dilaurylhydroxylamine, N,N-didodecylhydroxylamine, N,N-ditetradecylhydroxylamine, N,N-dihexadecylhydroxylamine, N,N-dioctadecylhydroxylamine, N-hexadecyl-N-tetradecylhydroxylamine, N-hexadecyl-N-heptadecylhydroxylamine, N-hexadecyl-N-octadecylhydroxylamine, N-heptadecyl-N-octadecylhydroxylamine, N-methyl-N-octadecylhydroxylamine, or N,N-di(C 16 -C 18 alkyl)hydroxylamine.

[0057] The amine oxide stabilizer is, for example, di(C 16 -C 18 )alkylmethylamine oxide, CAS#204933-93-7.

[0058] The combination of the organic phosphorus stabilizer and the dialkylhydroxylamine is, for example, tris(2,4-di-tert-butylphenyl)phosphite and N,N-di(C 16 -C 18 alkyl)hydroxylamine.

[0059] The combination of the organic phosphorus stabilizer and the amine oxide stabilizer is, for example, tris(2,4-di-tert-butylphenyl)phosphite and di(C 16 -C 18 )alkylmethylamine oxide.

[0060] The weight / weight ratio of these combinations can range from approximately 1 / 9, 1 / 8, 1 / 7, 1 / 6, 1 / 5, 1 / 4, 1 / 3, 1 / 2, or 1 / 1 to approximately 1 / 2, 1 / 3, 1 / 4, 1 / 5, 1 / 6, 1 / 7, 1 / 8, or 1 / 9.

[0061] The antioxidant may be present in total, based on the total weight of the hollow article, in any of the following amounts: approximately 0.05% by weight, approximately 0.10% by weight, approximately 0.20% by weight, approximately 0.30% by weight, approximately 0.40% by weight, approximately 0.50% by weight, or approximately 0.60% by weight, to approximately 0.70% by weight, approximately 0.80% by weight, approximately 0.90% by weight, approximately 1.0% by weight, approximately 1.5% by weight, or approximately 2.0% by weight.

[0062] Acid scavengers include hydrotalcite and amorphous basic aluminum magnesium carbonate, as described in U.S. Patents 4,427,816, 5,106,898, and 5,234,981. Hydrotalcite is also known as hycite, DHT4A, DHT4V, DHT4Z, DHT4A2, or DHT4C. Hydrotalcite can be natural or synthetic and may include coatings. Natural hydrotalcite has the structure Mg6Al2(OH) 16 It is maintained to contain CO3.4H2O. A typical empirical formula for synthetic hydrotalcite is Al2Mg 4.35 OH 11.36 CO 3(1.67) It is .x H2O. An example of a synthesis product is Mg 0.7 Al 0.3 (OH)2(CO3) 0.15 0.54H2O, Mg 4.5 Al2(OH) 13 CO3,35H2O, and Mg 4.2 Al(OH) 12.4 CO3 is one example.

[0063] In some embodiments, the acid scavenger includes metal salts of fatty acids, such as alkali or alkaline earth metal salts of fatty acids. In some embodiments, the acid scavenger includes calcium, magnesium, zinc, sodium, potassium, or aluminum salts of fatty acids. In some embodiments, the acid scavenger includes stearic acid, behenic acid, ricinoleic acid, or calcium palmitate, magnesium, zinc, sodium, potassium, or aluminum. In certain embodiments, the acid scavenger includes calcium stearate, zinc stearate, magnesium behenate, magnesium stearate, sodium ricinoleate, and potassium palmitate. In other embodiments, the acid scavenger includes zinc oxide.

[0064] In some embodiments, a combination of one or more acid scavengers may be used.

[0065] Acid scavengers may be present in total, based on the total weight of the article, at any of the following concentrations: approximately 50 ppm (parts per million), approximately 100 ppm, approximately 200 ppm, approximately 300 ppm, approximately 400 ppm, approximately 500 ppm, or approximately 600 ppm, to approximately 700 ppm, approximately 800 ppm, approximately 900 ppm, approximately 1000 ppm, approximately 1100 ppm, approximately 1200 ppm, approximately 1300 ppm, approximately 1400 ppm, approximately 1500 ppm, approximately 1600 ppm, approximately 1700 ppm, approximately 1800 ppm, approximately 1900 ppm, or approximately 2000 ppm.

[0066] In other embodiments, the hollow article may contain an acid scavenger in an amount ranging from about 0.1% by weight, about 0.2% by weight, or about 0.5% by weight, to about 1.0% by weight, about 1.5% by weight, about 2.0% by weight, about 2.5% by weight, or about 3.0% by weight, based on the total weight of the article.

[0067] Colorants, pigments, or fillers may also be added to this polyolefin substrate.

[0068] Pigments include inorganic pigments, such as effect pigments including metallic pigments such as the three crystalline forms of titanium dioxide: rutile, anatase, or brookite, ultramarine blue, iron oxide, bismuth vanadate, carbon black, and aluminum flakes, as well as pearlescent pigments such as mica, and organic pigments such as phthalocyanine, perylene, azo compounds, isoindoline, quinophthalone, diketopyrrolopyrrole, quinacridone, dioxazine, and indanthron. Pigments may be included alone or in any combination, typically in amounts up to about 5% by weight based on the total weight of the article. Dyes are any colorants that are completely soluble in the plastic used or present in a molecularly dispersed form, and can therefore be used to provide high permeability, non-diffusive coloring of the polymer. Other dyes are organic compounds that fluoresce in the visible portion of the electromagnetic spectrum, such as fluorescent dyes. Dyes may be included alone or in any combination, typically in amounts up to about 5% by weight based on the total weight of the article.

[0069] Particulate fillers may be present in any amount from about 0.01% by weight, about 0.1% by weight, about 1% by weight, about 5% by weight, about 10% by weight, about 15% by weight, or about 20% by weight, to about 25% by weight, about 30% by weight, about 35% by weight, about 40% by weight, about 45% by weight, or about 50% by weight, based on the total weight of the article. Fillers include, but are not limited to, titanium dioxide, silicon carbide, silica (and other silica oxides, whether precipitated or not), antimony oxide, lead carbonate, zinc oxide, lithopone, zircon, corundum, spinel, apatite, barite powder, barium sulfate, carbon black, dolomite, calcium carbonate, talc, as well as hydrotalcite compounds of Mg, Ca, or Zn ions and Al, Cr, or Fe ions, and hydrates or unhydrates of CO3 and / or HPO4, quartz powder, magnesium carbonate hydrochloride, glass fibers, clay, alumina, as well as other metal oxides and carbonates, metal hydroxides, chromium, phosphorus, antimony trioxide, silica, silicone, and blends thereof. These fillers may include any other fillers and porous fillers as well as supports known in the art.

[0070] Further additives, such as antistatic agents (antistats), scratch-resistant additives, slip-resistant agents, and polymer processing aids, may be incorporated into the polyolefin substrate (see Plastic Additives Handbook, 6th edition). These include metal salts of fatty acids, such as calcium stearate, magnesium stearate, zinc stearate, or aluminum stearate. Other additives include thioether additives, such as dilauryl thiodipropionate or distearyl thiodipropionate.

[0071] Further additives include benzofuranone stabilizers, such as U.S. Patent Nos. 4,325,863, 4,338,244, 5,175,312, 5,216,052, 5,252,643, 5,369,159, 5,356,966, 5,367,008, 5,428,177, or 5,428,162. , or also disclosed in U.S. Patent Application Publication No. 2012 / 0238677, including 3-[4-(2-acetoxyethoxy)phenyl]-5,7-di-tert-butyl-benzofuran-2-one, 5,7-di-tert-butyl-3-[4-(2-stearoyloxyethoxy)phenyl]benzofuran-2-one, 3,3'-bis[5,7-di-tert This includes -butyl-3-(4-[2-hydroxyethoxy]phenyl)benzofuran-2-one], 5,7-di-tert-butyl-3-(4-ethoxyphenyl)benzofuran-2-one, 3-(4-acetoxy-3,5-dimethylphenyl)-5,7-di-tert-butyl-benzofuran-2-one, 3-(3,5-dimethyl-4-pivaloyloxyphenyl)-5,7-di-tert-butyl-benzofuran-2-one, 3-(3,4-dimethylphenyl)-5,7-di-tert-butyl-benzofuran-2-one, 3-(2-acetyl-5-isooctylphenyl)-5-isooctylbenzofuran-2-one, and 3-(2,3-dimethylphenyl)-5,7-di-tert-butyl-benzofuran-2-one. Further additives may include compatibilizers or dispersants, such as maleic anhydride-grafted PE or PP, poly(ethylene-co-vinyl acetate), and poly(ethylene-acrylic acid). The further additives may be present in amounts ranging from about 0.05% by weight, 0.2% by weight, about 0.5% by weight, about 0.7% by weight, or about 1.0% by weight, to about 1.5% by weight, about 2.0% by weight, about 2.5% by weight, about 3.0% by weight, about 3.5% by weight, about 4.0% by weight, about 4.5% by weight, or about 5.0% by weight, based on the total weight of the article.

[0072] Rotational molding is used to manufacture fairly large hollow plastic articles that can be reinforced with glass fibers. The process involves filling one side of a mold with plastic material. The mold is then closed on the other side and heated and rotated in an oven, rotating around different axes, allowing the molten plastic to spread across the mold walls. After cooling, a hollow article is obtained. In this way, it is possible to manufacture, for example, a storage tank from HD polyethylene. In some embodiments, the process requires heating the polyolefin mixture to a temperature in the range of about 170°C, about 190°C, about 210°C, about 215°C, about 220°C, about 230°C, about 240°C, about 260°C, or about 280°C to about 300°C, about 340°C to about 370°C, or about 400°C or higher. These temperatures represent the peak internal air temperature (PIAT) of the oven.

[0073] In some embodiments, a 125 mil, 5-inch x 5-inch test sample of the hollow article may exhibit impact strengths of 21 ft / lb (feet / pound) or more, 23 ft / lbs or more, 25 ft / lbs or more, 27 ft / lbs or more, 29 ft / lbs or more, 31 ft / lbs or more, 33 ft / lbs or more, 35 ft / lbs or more, 37 ft / lbs or more, 39 ft / lbs or more, 40 ft / lbs or more, 41 ft / lbs or more, 42 ft / lbs, or 43 ft / lbs or more.

[0074] In certain embodiments, a 125 mil thick, 5-inch x 5-inch test sample of the hollow article may exhibit ductility of 50% or more, 55% or more, 60% or more, 65% or more, 70% or more, 75% or more, 80% or more, 85% or more, 90% or more, 95% or more, 96% or more, 97% or more, 98% or more, or 99% or more.

[0075] In certain other embodiments, a test sample of the hollow article with a thickness of 125 mils and an size of 5 inches x 5 inches yielded values ​​of 0.0 or less, -0.5 or less, -0.7 or less, -1.0 or less, -1.2 or less, -1.4 or less, It may exhibit a yellowness index (YI) of -1.6 or less, -1.8 or less, -2.0 or less, -2.2 or less, -2.4 or less, -2.6 or less, -2.7 or less, -2.8 or less, or -2.9 or less.

[0076] In some embodiments, a test sample of the hollow article with a thickness of 125 mils and an dimensions of 5 inches x 5 inches yielded values ​​of -3.0 or less, -3.3 or less, -3.5 or less, -3.7 or less, -3.9 or less, -4.0 or less, -4.1 or less, It may exhibit a yellowness index (YI) of -4.2 or less, -4.3 or less, -4.4 or less, or -4.5 or less.

[0077] In certain embodiments, a 125 mil thick, 5-inch x 5-inch test sample of the hollow article may exhibit an impact strength of 40 ft / lbs or more, ductility of 90% or more, and a YI of 0.0 or less, -1.0 or less, -1.5 or less, or -2.0 or less.

[0078] Mechanical properties can be determined according to the Association of Rotational Molders (ARM) Impact Test. The above embodiments relating to impact strength, ductility, and color can be determined in test samples of rotationally molded hollow articles with peak internal air temperatures of approximately 380°F, approximately 400°F, or approximately 420°F.

[0079] The incorporation of phosphonic acid esters, N-alkoxyhindered amines, melamine cyanurate (the additive), and any further additives into the polyolefin substrate is carried out by known methods, for example, before or after molding, with or without subsequent evaporation of the solvent, or by applying a dissolved or dispersed additive mixture to the polyolefin. The additive can also be added to the polyolefin in the form of a masterbatch, which contains the additive at a concentration of, for example, about 2.5% to about 40% by weight, based on the total weight of the masterbatch. In the form of a masterbatch, the polymer of the masterbatch does not need to be the same as that of the polyolefin substrate.

[0080] Molding is carried out using known mixers, such as mixers, kneaders, or extruders. This additive and any further additives may be pre-mixed or added individually. Furthermore, this additive and any further additives may be added before polymerization, during polymerization, or before crosslinking. This additive and any further additives may be incorporated into the polymer to make it flame-retardant in its pure form, or encapsulated in wax, oil, or the polymer.

[0081] Furthermore, this additive and any further additives can be sprayed onto a polyolefin substrate. They can be sprayed onto the polyolefin together with other additives or their melts after dilution. Spraying during the deactivation of the polymerization catalyst may be advantageous, and for example, spraying can be carried out using the vapor used for deactivation.

[0082] In some embodiments, the process includes weighing the raw materials and subsequently drying and blending the components. In certain embodiments, the additive and any further additives are incorporated into a thermoplastic polyolefin substrate by melt blending in an extruder. The additive and any additional additives may be added together or separately. In some embodiments, the term “incorporation into polyolefin” means melt blending, i.e., subjecting the mixture to melting conditions at a high temperature.

[0083] The mixture may be fed at a constant rate into a melting and mixing device such as an extruder to extrude the material into a desired form, such as pellets. The pellets are "fully compounded polyolefin substrates." Before rotational molding, the pellets may be ground to small, generally uniform particle sizes, for example, an average particle size of about 150 microns to about 500 microns.

[0084] The fully compounded polyolefin particles are filled into one side of a mold, and then closed with the other side. The mold is typically made of aluminum or steel. The closed mold is heated and rotated around different axes, causing the molten polymer to coat the inside of the mold. This process is called "sintering." The mold is then cooled, and the molded article is removed.

[0085] In addition to storage tanks, a number of other items, such as kayaks, toys, waste containers, and equipment housings, can be manufactured using the rotational molding process. Rotationally molded articles can often have relatively large average wall thicknesses. In some embodiments, the rotationally molded articles have average wall thicknesses of approximately 1.50 mm or more, approximately 1.75 mm or more, approximately 2.00 mm or more, approximately 2.25 mm or more, approximately 2.50 mm or more, approximately 2.75 mm or more, approximately 3.00 mm or more, approximately 3.25 mm or more, approximately 3.50 mm or more, approximately 3.75 mm or more, approximately 4.00 mm or more, approximately 4.25 mm or more, approximately 4.50 mm or more, or approximately 4.75 mm or more. In some embodiments, the rotationally molded article has an average wall thickness of approximately 1.50 mm, 1.75 mm, 2.00 mm, 2.25 mm, 2.50 mm, 2.75 mm, or 3.00 mm, ranging from approximately 3.25 mm, 3.50 mm, 3.75 mm, 4.00 mm, 4.25 mm, 4.50 mm, 4.75 mm, 5.00 mm, 5.25 mm, 5.50 mm, 5.75 mm, or 6.00 mm.

[0086] In this specification, the articles “a” and “an” refer to one or more grammatical objects (e.g., at least one). All scopes cited herein are inclusive. The term “about” as used throughout is used to express and describe small variations. For example, “about” means that a number is changed by ±5%, ±4%, ±3%, ±2%, ±1%, ±0.5%, ±0.4%, ±0.3%, ±0.2%, ±0.1%, or ±0.05%. All numbers are modified by the term “about,” whether explicitly indicated or not. Numbers modified by the term “about” include a specific identified value. For example, “about 5.0” includes 5.0.

[0087] The U.S. patents, U.S. patent applications, and published U.S. patent applications discussed herein are incorporated herein by reference. [Examples]

[0088] Unless otherwise specified, all parts and percentages are by weight. Unless otherwise specified, weight percentages (weight%) are based on the entire composition, excluding any volatile substances.

[0089] Example 1 The additive is low-density polyethylene (LDPE, 0.935 g / cm³). 3 ) are dry-blended to provide the formulation. Additive levels are reported in parts per million by weight, based on the weight of polyethylene. The dry-blend is melt-extruded into pellets, ground to 35 mesh, and placed in a laboratory-scale FST M20 "clamshell" aluminum mold. The mold is rotated on two axes in a gas-fired oven. While the temperature rises, hot air is circulated in the chamber by a blower to provide a peak internal air temperature (PIAT) of 400°F or 420°F. The temperature is maintained for 20 minutes. The oven is opened and cooled for 24 minutes while still rotating. The mold is opened and the hollow article is removed.

[0090] The control formulation contains no additives. Each of formulations 1-4 contains 400 ppm tris(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate (phenolic antioxidant) and 600 ppm N,N-di(C) 16 -C 18 Alkyl)hydroxylamine (hydroxylamine stabilizer), 1200 ppm tris(2,4-di-tert-butylphenyl) phosphite (organophosphorus stabilizer), 1200 ppm 4,4'-hexamethylenebis(amino-2,2,6,6-tetramethylpiperidine) and 2,4-dichloro-6-[(2,2,6,6-tetramethylpiperidine-4-I) end-capped with 2-chloro-4,6-bis(dibutylamino)-s-triazine Formulas 2-4 contain an oligomer condensate of butylamino-s-triazine (hindered amine light stabilizer), 400 ppm of N'-(2-ethoxyphenyl)-N-(2-ethylphenyl)oxamide (oxamide UV absorber), 400 ppm of hydrotalcite (acid scavenger), and 200 ppm of zinc stearate (acid scavenger). Formulas 2-4 also contain an additional 500 ppm of thioether additives as outlined below. Thio-1 is distearyl thiodipropionate. Thio-2 is pentaerythritol tetrakis (β-lauryl thiopropionate). Thio-3 is distearyl disulfide. The weight of the additives is in ppm (parts per million) based on the weight of polyethylene. Formulation: Thio1, Thio2, Thio3 Contrast ---- ---- ---- 1 ---- ---- ---- 2,500 ---- ---- 3 ---- 500 ---- 4 ---- ---- 500

[0091] The tested samples were 125 mils thick (3.175 mm) according to the Association of Rotational Molders (ARM) Impact Test. The samples were tested for impact strength, ductility, and color formation. Impact strength is reported in feet / pounds (ft / lbs). Ductility is reported in percent (%). Color is reported as YI. The results for samples of hollow articles prepared at peak internal air temperatures of 400°F and 420°F are as follows: PIAT=400°F Composition, Impact Strength, Ductility, Color (YI) Control 7.8 0 -1.5 1 39.3 94 -1.0 2 43.4 100 -4.5 3 36.1 83 -4.5 4 38.7 94 -4.6 PIAT=420°F Composition, Impact Strength, Ductility, Color (YI) Control 7.8 0 -2.0 1 20.6 56 0.5 2 43.4 100 -2.0 3 29.2 72 -2.9 4 21.8 50 -2.4

Claims

1. A plastic article comprising a polyolefin substrate and an additive incorporated into the polyolefin substrate, which is stabilized against the harmful effects of heat, light, and oxygen, wherein the additive is i) Hindered amine light stabilizers, ii) UV absorbers, and iii) Contains thioether additives, A plastic article having a hollow portion within it.

2. The aforementioned hindered amine light stabilizer, (1) 1-Cyclohexyloxy-2,2,6,6-tetramethyl-4-octadecylaminopiperidine, (2) Bis(2,2,6,6-tetramethylpiperidine-4-yl) sebacate, (3) Bis(1-acetoxy-2,2,6,6-tetramethylpiperidine-4-yl) sebacate, (4) Bis(1,2,2,6,6-pentamethylpiperidine-4-yl) sebacate, (5) Bis(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidine-4-yl) sebacate, (6) Bis(1-octyloxy-2,2,6,6-tetramethylpiperidine-4-yl) sebacate, (7) Bis(1-acyl-2,2,6,6-tetramethylpiperidine-4-yl) sebacate, (8) Bis(1,2,2,6,6-pentamethyl-4-piperidyl)n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate, (9) 2,4-bis[(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidine-4-yl)butylamino]-6-(2-hydroxyethylamino-s-triazine, (10) Bis(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidine-4-yl) adipate, (11) 2,4-bis[(1-cyclohexyloxy-2,2,6,6-piperidine-4-yl)butylamino]-6-chloro-s-triazine, (12) 1-(2-hydroxy-2-methylpropoxy)-4-hydroxy-2,2,6,6-tetramethylpiperidine, (13) 1-(2-hydroxy-2-methylpropoxy)-4-oxo-2,2,6,6-tetramethylpiperidine, (14) 1-(2-hydroxy-2-methylpropoxy)-4-octadecanoyloxy-2,2,6,6-tetramethylpiperidine, (15) Bis(1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidine-4-yl) sebacate, (16) Bis(1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidine-4-yl) adipate, (17) 2,4-bis{N-[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidine-4-yl]-N-butylamino}- 6-(2-hydroxyethylamino)-s-triazine, (18) 4-benzoyl-2,2,6,6-tetramethylpiperidine, (19) Di-(1,2,2,6,6-pentamethylpiperidine-4-yl) p-methoxybenzylidenemalonate, (20) 2,2,6,6-tetramethylpiperidine-4-yloctadecanoate, (21) Bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl) succinate, (22) 1,2,2,6,6-pentamethyl-4-aminopiperidine, (23) 2-undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxospiro[4,5]decane, (24) Tris(2,2,6,6-tetramethyl-4-piperidyl)nitrilotriacetate, (25) Tris(2-hydroxy-3-(amino-(2,2,6,6-tetramethylpiperidine-4-yl)propyl) nitrilotriacetate, (26) Tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butane-tetracarboxylate, (27) Tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)-1,2,3,4-butane-tetracarboxylate, (28) 1,1'-(1,2-ethanediyl)-bis(3,3,5,5-tetramethylpiperazinone), (29) 3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione, (30) 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione, (31) 3-dodecyl-1-(2,2,6,6-tetramethyl-4-piperidyl)pyrrolidine-2,5-dione, (32) 3-dodecyl-1-(1,2,2,6,6-pentamethyl-4-piperidyl)pyrrolidine-2,5-dione, (33) N,N'-bis-formyl-N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine, (33a) Bis(1-undecanyloxy-2,2,6,6-tetramethylpiperidine-4-yl) carbonate, (34) 2,4-bis[(1-cyclohexyloxy-2,2,6,6-piperidine-4-yl)butylamino]-6-chloro-s- Reaction product of triazine and N,N'-bis(3-aminopropyl)ethylenediamine, (35) Condensate of 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, (36) N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)-hexamethylenediamine and 4-tert- Octylamino-2,6-dichloro-1,3,5-triazine condensate, (37) Condensate of N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)-hexamethylenediamine and 4-cyclohexylamino-2,6-dichloro-1,3,5-triazine, (38) Condensate of N,N'-bis-(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and 4-morpholino-2,6-dichloro-1,3,5-triazine, (39) N,N'-bis-(1,2,2,6,6-pentamethyl-4-piperidyl)hexamethylenediamine and 4- Condensate of morpholino-2,6-dichloro-1,3,5-triazine, (40) 2-chloro-4,6-bis(4-n-butylamino-2,2,6,6-tetramethylpiperidyl)-1,3,5-triazine and condensates of 1,2-bis(3-aminopropylamino)ethane, (41) Condensate of 2-chloro-4,6-di-(4-n-butylamino-1,2,2,6,6-pentamethylpiperidyl)-1,3,5-triazine and 1,2-bis-(3-aminopropylamino)ethane, (42) Reaction product of 7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospiro[4,5]decane and epichlorohydrin, (43) poly[methyl,(3-oxy-(2,2,6,6-tetramethylpiperidine-4-yl)propyl)]siloxane, CAS#182635-99-0, (44) Maleic anhydride - C １８ -C ２２－ α-olefin copolymer and 2,2,6,6- Reaction product with tetramethyl-4-aminopiperidine, (45) Oligomer condensates of 2,4-dichloro-6-[(2,2,6,6-tetramethylpiperidine-4-yl)butylamino]-s-triazine, end-capped with 4,4'-hexamethylenebis(amino-2,2,6,6-tetramethylpiperidine) and 2-chloro-4,6-bis(dibutylamino)-s-triazine, (46) 4,4'-Hexamethylenebis(amino-1,2,2,6,6-pentamethylpiperidine) and an oligomeric condensate of 2,4-dichloro-6-[(1,2,2,6,6-pentamethylpiperidine-4-yl)butylamino]-s-triazine end-capped with 2-chloro-4,6-bis(dibutylamino)-s-triazine, (47) 2,4-dichloro-6-[(1-propoxy-2,2,6,6-tetramethylpiperidine-4-yl)butylamino]-s-, end-capped with 4,4'-hexamethylenebis(amino-1-propoxy-2,2,6,6-tetramethylpiperidine-4-yl)butylamino]-s- Triazine oligomeric condensates, (48) 2,4-dichloro-6-[(1-acyloxy-2,2,6,6-tetramethylpiperidine-4-yl)butylamino]-s-, end-capped with 4,4'-hexamethylenebis(amino-1-acyloxy-2,2,6,6-tetramethylpiperidine-4-yl)butylamino]-s- Triazine oligomeric condensates, and (49) A product obtained by reacting (a) with (b), wherein (a) is a product obtained by reacting 1,2-bis(3-aminopropylamino)ethane with cyanuric acid chloride, The plastic article according to claim 1, wherein (b) is selected from the group consisting of products, wherein (b) is (2,2,6,6-tetramethylpiperidine-4-yl)butylamine.

3. The plastic article according to claim 1 or 2, wherein the ultraviolet stabilizer is selected from the group consisting of oxamide, hydroxyphenylbenzotriazole, tris-aryl-s-triazine, hydroxybenzoate, 2-hydroxybenzophenone, and cyanoacrylate ultraviolet absorbers.

4. The thioether additive is, 【Chemistry 1】 A plastic article according to any one of claims 1 to 3, comprising a mercaptan-containing compound containing one or more portions of the above.

5. The thioether additive is, 【Chemistry 2】 A plastic article according to any one of claims 1 to 4, comprising a mercaptan-containing compound containing one or more portions of the formula, wherein R is a hydrocarbyl group.

6. The thioether additive is, 【Transformation 3】 The plastic article according to any one of claims 1 to 5, wherein each R in the formula is independently a hydrocarbyl group.

7. The plastic article according to any one of claims 1 to 6, wherein the thioether additive comprises a disulfide-containing compound of formula R-S-S-R, where each R is independently a hydrocarbyl group.

8. The plastic article according to any one of claims 1 to 7, wherein the polyolefin substrate includes polyethylene.

9. The plastic article according to any one of claims 1 to 8, wherein the article contains approximately 50% to approximately 95% by weight of polyolefin, based on the total weight of the article.

10. The plastic article according to any one of claims 1 to 9, wherein the article contains the hindered amine light stabilizer in an amount of about 50 ppm by weight to about 2000 ppm by weight, based on the total weight of the article.

11. The plastic article according to any one of claims 1 to 10, wherein the article contains the ultraviolet absorber in an amount of about 50 ppm by weight to about 2000 ppm by weight, based on the total weight of the article.

12. The plastic article according to any one of claims 1 to 11, wherein the article contains the thioether additive in an amount of about 50 ppm by weight to about 2000 ppm by weight, based on the total weight of the article.

13. The plastic article according to any one of claims 1 to 12, wherein the weight / weight ratio of the hindered amine light stabilizer to the thioether additive is about 7 / 1 to about 1 / 1.

14. The plastic article according to any one of claims 1 to 13, wherein the weight / weight ratio of the ultraviolet absorber to the thioether additive is about 3 / 1 to about 1 / 3.

15. The plastic article according to any one of claims 1 to 14, wherein the article further comprises one or more additives selected from the group consisting of phenolic antioxidants, hydroxylamine stabilizers, organophosphorus stabilizers, and acid scavengers.

16. The plastic article according to any one of claims 1 to 15, wherein the article comprises one or more fillers in an amount of about 0.1% to about 50% by weight, based on the total weight of the article.

17. The plastic article according to any one of claims 1 to 16, wherein the article has an average wall thickness of about 1.50 mm to about 6.00 mm.

18. The plastic article according to any one of claims 1 to 17, wherein a test sample of the article with a thickness of 125 mils and measuring 5 inches x 5 inches exhibits an impact strength of 21 ft / lbs or more.

19. The plastic article according to any one of claims 1 to 18, wherein a test sample of the article with a thickness of 125 mils and measuring 5 inches x 5 inches exhibits ductility of 50% or more.

20. The plastic article according to any one of claims 1 to 19, wherein a test sample of the article, with a thickness of 125 mils and measuring 5 inches x 5 inches, exhibits a yellowness index (YI) of -2.0 or less.

21. A process for producing hollow plastic articles, i) a hindered amine light stabilizer, ii) an ultraviolet absorber, and iii) a thioether additive are incorporated into a polyolefin substrate to provide a fully compounded polyolefin mixture. A process comprising: adding the mixture to a mold; heating the mold to a temperature exceeding 280°C; rotating the mold around at least two axes so that the molten polyolefin mixture coats the inside of the mold; cooling the mold while still rotating it; opening the mold; and removing the formed hollow article.

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