Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
  • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
  • B65D1/00—Containers having bodies formed in one piece, e.g. by casting metallic material, by moulding plastics, by blowing vitreous material, by throwing ceramic material, by moulding pulped fibrous material, by deep-drawing operations performed on sheet material
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
  • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
  • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
  • C08G63/16—Dicarboxylic acids and dihydroxy compounds
  • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
  • C08G63/181—Acids containing aromatic rings
  • C08G63/183—Terephthalic acids
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J3/00—Processes of treating or compounding macromolecular substances
  • C08J3/20—Compounding polymers with additives, e.g. colouring
  • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
  • C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
  • C08K5/43—Compounds containing sulfur bound to nitrogen
  • C08K5/435—Sulfonamides
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
  • C08K5/45—Heterocyclic compounds having sulfur in the ring
  • C08K5/46—Heterocyclic compounds having sulfur in the ring with oxygen or nitrogen in the ring
  • C08K5/47—Thiazoles
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
  • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
  • C08L67/03—Polyesters derived from dicarboxylic acids and dihydroxy compounds the dicarboxylic acids and dihydroxy compounds having the carboxyl- and the hydroxy groups directly linked to aromatic rings
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
  • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers

Definitions

• the present invention relates to a method for producing a plastic bottle. Specifically, a masterbatch containing a polyester resin and 1,2-benzisothiazol-3 (2H) -one 1,1-dioxide compound is prepared, and the masterbatch is prepared. The present invention relates to a method for producing a plastic bottle by mixing with a polyester resin and molding the mixture.
• Polyester resins have many properties such as excellent transparency, gas barrier properties, mechanical properties, heat resistance, and light weight.
• polyethylene terephthalate resins are used in various soft drink fields such as carbonated water and mineral water. It has grown rapidly with increasing demand and is used in a wide range of fields.
• polyethylene terephthalate resin is ejected (extruded) into a mold, and a preform (preliminarily molded product) is injected.
• a preform preliminarily molded product
• Molding is performed, the mouth of the molded test tubular preform is heated to crystallize, and the preform is placed in the blow mold of a blow molding machine and supported by the mouth,
• a predetermined plastic bottle is formed by blow molding, and then cooled and removed from the mold to obtain a predetermined plastic bottle.
• polyethylene terephthalate is a crystalline resin
• the crystallization speed is extremely slow, so that the range of molding conditions is extremely narrow and the molding cycle of plastic bottles is long.
• a method of adding a nucleating agent As a method for improving the crystallization speed, a method of adding a nucleating agent is generally known.
• a nucleating agent include polymers, ores, metal salts of organic acids or inorganic acids, powdered glass, powdered metals, and the like.
• olefins such as low density polyethylene, high density polyethylene and linear low density polyethylene, ores (clay) such as graphite, talc and kaolin, metal oxides such as zinc oxide, alumina and magnesium oxide, silica, Silica compounds such as calcium silicate and magnesium silicate, metal carbonates such as magnesium carbonate, calcium carbonate, sodium carbonate and potassium carbonate, barium sulfate, calcium sulfate, sodium benzoate, p-tert-butylaluminum benzoate, aromatic phosphoric acid Ester metal salts, dibenzylidene sorbitol and sulfonamide compounds, etc. It is below.
• Patent Document 2 proposes a polyester resin composition in which a metal salt of a sulfonamide compound is added to polyethylene terephthalate resin as a powder.
• an object of the present invention is to solve the above-mentioned problems of the prior art, to provide a method for producing a plastic bottle that has improved molding cycles, has few coloring problems such as whitening, and is excellent in transparency.
• the present inventors added 1,2-benzisothiazol-3 (2H) -one 1,1-dioxide compound to the polyester resin by a masterbatch method. As a result, the inventors have found that the above object can be achieved and have completed the present invention.
• the method for producing a plastic bottle of the present invention refers to 1,5-benzisothiazol-3 (2H) -one 1,1-dioxide compound in an amount of 0.005 to 0.025 parts by mass with respect to 100 parts by mass of the polyester resin.
• 1,2-benzisothiazol-3 (2H) -one 1,1-dioxide compound in an amount of 0.01 to 0.5 parts by mass per 100 parts by mass of the polyester resin
• the masterbatch containing is prepared, then the masterbatch and the polyester resin are mixed to prepare a mixture, and the mixture is formed into a bottle shape.
• the 1,2-benzisothiazol-3 (2H) -one 1,1-dioxide compound is represented by the following general formula (1), Wherein A is a halogen atom, an alkyl group having 1 to 8 carbon atoms which may have a substituent, an alkoxy group having 1 to 8 carbon atoms which may have a substituent, or 1 to 5 represents an alkylthio group, a nitro group, or a cyano group, and A may be different from each other, m represents an integer of 0 to 4, X represents a metal atom, and n represents an integer of 1 to 4. Wherein n represents an integer corresponding to the valence of the metal atom represented by X), and in the general formula (1), X is sodium. , N is preferably 1.
• the mixture of the master batch and the polyester resin is molded into a bottle shape by blow molding.
• a cylindrical preform may be produced by injection molding the mixture of the master batch and the polyester resin, and the preform may be molded into a bottle shape by blow molding. preferable.
• the preform is heated and crystallized, and then the preform is molded into a bottle shape by blow molding.
• the produced plastic bottle is a heat-resistant plastic bottle.
• the present invention relates to the stretching of plastic bottles by mixing a masterbatch containing 1,2-benzisothiazol-3 (2H) -one 1,1-dioxide compound with a polyester resin and using it for the production of plastic bottles.
• the molding cycle can be improved without deteriorating the transparency of the part and the yellowness.
• polyester resin used in the present invention examples include polyalkylene terephthalate such as polyethylene terephthalate, polybutylene terephthalate, polycyclohexanedimethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, or aromatic polyester containing polyalkylene naphthalate; Ether ester resins; degradable aliphatic polyesters such as polyhydroxybutyrate, polycaprolactone, polybutylene succinate, polyethylene succinate, polylactic acid resin, polymalic acid, polyglycolic acid, polydioxanone, poly (2-oxetanone); aromatic Examples include polyester / polyether block copolymers, aromatic polyester / polylactone block copolymers, polyarylate, etc. But polyethylene terephthalate and polybutylene terephthalate, since transparency is good, is preferably used.
• the polyester resin may be a single resin or a blend of a plurality of resins (for example, a blend of polyethylene terephthalate and polybutylene terephthalate), or a copolymer thereof (for example, a polyester of polybutylene terephthalate and polytetramethylene glycol). May be a polyester resin comprising a polyether copolymer.
• the polyethylene terephthalate resin suitable in the present invention is obtained by subjecting terephthalic acid and ethylene glycol to an esterification reaction or by subjecting a product obtained by transesterifying dimethyl terephthalate and ethylene glycol to a polycondensation reaction.
• the polycondensation reaction is usually carried out at a temperature of 265 to 300 ° C., preferably 270 to 290 ° C. under a reduced pressure of 1 hectopascal.
• this process may be a batch type or a continuous type.
• an acid component and / or a glycol component can be contained as a copolymer component within a range not losing characteristics.
• the acid component include isophthalic acid, adipic acid, sebacic acid, glutaric acid, diphenylmethane dicarboxylic acid, dimer acid, 2,6-naphthalenedicarboxylic acid, 4,4′-biphenyldicarboxylic acid, and the like.
• the 1,2-benzisothiazol-3 (2H) -one 1,1-dioxide compound used in the present invention includes 1,2-benzisothiazol-3 (2H) -one 1,1-dioxide, 2-benzisothiazol-3 (2H) -one 1,1-dioxide salt, 1,2-benzisothiazol-3 (2H) -one 1,1-dioxide halide, 1,2-benzisothiazole -3 (2H) -one 1,1-dioxide derivatives and the like, specifically, for example, 1,2-benzisothiazol-3 (2H) -one 1,1-dioxide, 1,2-benziso Thiazol-3 (2H) -one 1,1-dioxide sodium, 1,2-benzisothiazol-3 (2H) -one 1,1-dioxide potassium, 1,2-benzisothiazole-3 2H) -one 1,1-dioxide calcium, thio 1,2-benzisothiazole-3 (2H) -one 1,1-di
• the 1,2-benzisothiazol-3 (2H) -one 1,1-dioxide compound used in the present invention is represented by the following general formula (1), Wherein A is a halogen atom, an alkyl group having 1 to 8 carbon atoms which may have a substituent, an alkoxy group having 1 to 8 carbon atoms which may have a substituent, or 1 to 5 represents an alkylthio group, a nitro group, or a cyano group, and A may be different from each other, m represents an integer of 0 to 4, X represents a metal atom, and n represents an integer of 1 to 4. Wherein n represents an integer corresponding to the valence of the metal atom represented by X), and may include hydrates.
• the 1,2-benzisothiazol-3 (2H) -one 1,1-dioxide compound is used in an amount of 0.005 to 0.025 parts by mass with respect to 100 parts by mass of the polyester resin.
• Examples of the halogen atom represented by A in the general formula (1) include fluorine, chlorine, bromine, iodine and the like.
• Examples of the alkyl group having 1 to 8 carbon atoms which may have a substituent represented by A in the general formula (1) include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, and sec-butyl. , Isobutyl, amyl, isoamyl, tertiary amyl, hexyl, cyclohexyl, heptyl, isoheptyl, tertiary heptyl, n-octyl, isooctyl, tertiary octyl, 2-ethylhexyl, trifluoromethyl, etc.
• a hydrogen atom in the group may be substituted with a halogen atom.
• alkoxy group having 1 to 8 carbon atoms which may have a substituent represented by A in the general formula (1) include methoxy, ethoxy, propoxy, isopropoxy, butoxy, second butoxy, third Examples include butoxy and trifluoromethyloxy, and a hydrogen atom in these groups may be substituted with a halogen atom.
• a in the general formula (1) includes alkylthio groups such as methylthio, ethylthio, propylthio, isopropylthio, tert-butylthio, nitro group, cyano group, etc. in addition to the above alkyl groups and alkoxy groups.
• Examples of the metal atom represented by X in the general formula (1) include metal atoms such as lithium, potassium, sodium, magnesium, calcium, strontium, barium, titanium, manganese, iron, zinc, silicon, zirconium, and yttrium.
• metal atoms such as lithium, potassium, sodium, magnesium, calcium, strontium, barium, titanium, manganese, iron, zinc, silicon, zirconium, and yttrium.
• potassium, lithium, and sodium are preferable because they are excellent in the crystallization promoting effect of the polyester resin, and sodium is particularly preferable.
• Preferred examples of the compound represented by the general formula (1) include the following compound No. 1-No. However, the present invention is not limited to these compounds.
• the 1,2-benzisothiazol-3 (2H) -one 1,1-dioxide compound is 0.005 to 0 with respect to 100 parts by mass of the polyester resin. 0.025 parts by mass is blended. When the amount is less than 0.005 parts by mass, the effect of addition is insufficient. When the amount is more than 0.025 parts by mass, the plastic bottle may crystallize excessively and become cloudy, and transparency may be impaired.
• polyester resin composition may be added to the polyester resin composition as necessary within a range in which the polyester resin characteristics as the main component are not practically changed.
• the other additive examples include, for example, an antioxidant made of phenol, phosphorus, sulfur, etc .; a light stabilizer made of HALS, UV absorber, etc .; hydrocarbon, fatty acid, aliphatic alcohol, fat Lubricants such as aliphatic ester compounds, aliphatic amide compounds, aliphatic carboxylic acid metal salts or other metal soaps; heavy metal deactivators; antifogging agents; cationic surfactants, anionic surfactants, Antistatic agents comprising nonionic surfactants, amphoteric surfactants, etc .; halogen compounds; phosphate compounds; phosphate amide compounds; melamine compounds; fluororesins or metal oxides; (poly) melamine phosphate , Flame retardants such as (poly) phosphate piperazine; fillers such as glass fiber and calcium carbonate; anti-blocking agents; slip agents; pigments; hydrotalcite, fumed Jamaica, fine particle silica, silica, diatomaceous earth, clay
• Silicate-based inorganic additives such as dibenzylidene sorbitol, bis (p-methylbenzylidene) sorbitol, bis (p-ethylbenzylidene) sorbitol, disodium bicyclo [2.2.1] heptane-2,3-dicarboxylate, etc.
• a crystal nucleating agent is mentioned.
• phenol-based antioxidant examples include 2,6-ditert-butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, stearyl (3,5-ditert-butyl-4- Hydroxyphenyl) propionate, distearyl (3,5-ditert-butyl-4-hydroxybenzyl) phosphonate, tridecyl 3,5-ditert-butyl-4-hydroxybenzylthioacetate, thiodiethylenebis [(3,5 -Di-tert-butyl-4-hydroxyphenyl) propionate], 4,4'-thiobis (6-tert-butyl-m-cresol), 2-octylthio-4,6-di (3,5-di-tert-butyl) -4-hydroxyphenoxy) -s-triazine, 2,2'-methylenebis (4-methyl-6-tert-butylphenol), bis [3,3 Bis (4-hydroxy-3-tert-but
• Examples of the phosphorus antioxidant include triphenyl phosphite, tris (2,4-ditertiarybutylphenyl) phosphite, tris (2,5-ditertiarybutylphenyl) phosphite, and tris (nonylphenyl).
• Phosphite tris (dinonylphenyl) phosphite, tris (mono, dimixed nonylphenyl) phosphite, diphenyl acid phosphite, 2,2'-methylenebis (4,6-ditert-butylphenyl) octyl phosphite , Diphenyldecyl phosphite, diphenyloctyl phosphite, di (nonylphenyl) pentaerythritol diphosphite, phenyl diisodecyl phosphite, tributyl phosphite, tris (2-ethylhexyl) phosphite, tridecyl phosphite, trilauryl phosphat , Dibutyl acid phosphite, dilauryl acid phosphite, trilauryl trithiopho
• sulfur-based antioxidant examples include dialkylthiodipropionates such as dilauryl, dimyristyl, myristylstearyl and distearyl esters of thiodipropionic acid and polyols such as pentaerythritol tetra ( ⁇ -dodecyl mercaptopropionate).
• dialkylthiodipropionates such as dilauryl, dimyristyl, myristylstearyl and distearyl esters of thiodipropionic acid
• polyols such as pentaerythritol tetra ( ⁇ -dodecyl mercaptopropionate).
• HALS examples include 1,2,2,6,6-pentamethyl-4-piperidyl stearate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, and bis (1-octoxy).
• -2,2,6,6-tetramethyl-4-piperidyl) sebacate 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate, 2,2,6,6-tetramethyl-piperidyl methacrylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) Bis (tridecyl) -1,2,3,4-butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) -2-butyl- -(3,5-ditert-butyl-4-hydroxybenzyl) malonate
• ultraviolet absorber examples include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, and 5,5′-methylenebis (2-hydroxy-4-methoxybenzophenone).
• 2-hydroxybenzophenones such as 2-; 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2-hydroxy-3, 5-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3,5 -Dicumylphenyl) benzotriazole, 2,2'-methylenebis (4- 3-octyl-6-benzotriazolylphenol), 2- (2-hydroxy-3-tert-butyl-5-carboxyphenyl) benzotriazole polyethylene glycol ester, 2- [2-hydroxy-3- (2-acryloyl) Oxyethyl) -5-methylphenyl] benzotriazole, 2- [2-hydroxy-3- (2-methacryloyloxyethyl) -5-
• Examples of the aliphatic amide compound used as the lubricant include monofatty acid amides such as lauric acid amide, stearic acid amide, oleic acid amide, erucic acid amide, ricinoleic acid amide, and 12-hydroxystearic acid amide; N, N '-Ethylenebislauric acid amide, N, N'-methylenebisstearic acid amide, N, N'-ethylenebisstearic acid amide, N, N'-ethylenebisoleic acid amide, N, N'-ethylenebisbehenic acid Amide, N, N′-ethylenebis-12-hydroxystearic acid amide, N, N′-butylene bisstearic acid amide, N, N′-hexamethylene bisstearic acid amide, N, N′-hexamethylene bisoleic acid N, N′-, such as amide, N, N′-xylylene bis-stearic acid amide Fatty acid amides; alkylo
• Examples of the flame retardant include phosphorus such as triphenyl phosphate, phenol / resorcinol / phosphorus oxychloride condensate, phenol / bisphenol A / phosphorus oxychloride condensate, 2,6-xylenol / resorcinol / phosphorus oxychloride condensate, etc.
• phosphorus such as triphenyl phosphate, phenol / resorcinol / phosphorus oxychloride condensate, phenol / bisphenol A / phosphorus oxychloride condensate, 2,6-xylenol / resorcinol / phosphorus oxychloride condensate, etc.
• Acid esters Phosphoric amides such as aniline / phosphorus oxychloride condensate, phenol / xylylenediamine / phosphorus oxychloride condensate; phosphazenes; halogen flame retardants such as decabromodiphenyl ether and tetrabromobisphenol A; melamine phosphate, phosphorus Phosphate salts of nitrogen-containing organic compounds such as acid piperazine, melamine pyrophosphate, piperazine pyrophosphate, melamine polyphosphate, piperazine polyphosphate; red phosphorus and surface-treated or microencapsulated red phosphorus; antimony oxide, zinc borate, etc. Flame retardant aids; Li tetrafluoroethylene, anti-drip agents such as silicone resins. Relative to the polyester to 100 parts by mass, preferably 1 to 30 parts by weight, more preferably 5 to 20 parts by weight is used.
• a method of blending the polyester resin with 1,2-benzisothiazol-3 (2H) -one 1,1-dioxide compound is a master batch.
• a method of blending a 1,2-benzisothiazol-3 (2H) -one 1,1-dioxide compound during the polycondensation reaction of the polyester resin can be used.
• the time of the polycondensation reaction of the polyester resin may be either before the start of the polyester polycondensation reaction or during the polycondensation reaction.
• the method of blending at the time of the polycondensation reaction of the polyester resin does not require the molding process of the polyester resin, so there is no acetaldehyde odor due to the thermal decomposition of the polyester resin accompanying the molding process of the polyester resin. Also preferred. Further, addition during the polycondensation reaction is preferable because the heat history is reduced including the case of not passing through the master batch.
• 1,2-benzisothiazol-3 (2H) -one 1,1-dioxide compound As a method of blending the 1,2-benzisothiazol-3 (2H) -one 1,1-dioxide compound during the polycondensation reaction of such a polyester resin, a slurry method can be mentioned, and 1,2-benzisothiazole- An example is a method in which a 3 (2H) -one 1,1-dioxide compound is dissolved in a solvent and added during a polycondensation reaction of a polyester resin.
• the solvent for dissolving the 1,2-benzisothiazol-3 (2H) -one 1,1-dioxide compound those capable of dissolving the glycol component or those that do not adversely affect the polycondensation reaction of polyethylene terephthalate are preferable.
• ethylene glycol is preferable.
• plastic molding methods can be used for molding the plastic bottle in the present invention.
• a blow molding method the direct blow method which performs blow molding after shaping
• a hot parison method one-stage method in which blow molding is continuously performed after preform molding
• a cold parison method in which the preform is cooled and taken out and then heated again to perform blow molding.
• Any of the two-stage methods can be employed, but in the present invention, it is particularly preferable to use the cold parison method.
• a preform obtained by injection molding or extrusion molding is heated to 65 to 130 ° C., preferably 70 to 110 ° C., and blow molded to obtain a blow molded bottle. If the preheating temperature of the preform is lower than 65 ° C., the softening is insufficient and blowing cannot be performed. If the preheating temperature is higher than 130 ° C. or the preheating time is too long, crystallization of the preform proceeds. However, the moldability and transparency may be lowered.
• Plastic bottles can improve the mechanical strength and heat resistance of the mouth by crystallizing the mouth. If the crystallization of the mouth is insufficient, the mouth may be deformed when capping the plastic bottle, the liquid will leak after cooling the plastic bottle filled with the liquid, or the cap will be loosened. May occur.
• the mouth portion As a method for crystallizing the mouth portion, it can be crystallized by heating the mouth portion of a preform or a plastic bottle before blow molding or after blow molding.
• the temperature for heat crystallization is preferably 160 to 200 ° C., more preferably 160 to 180 ° C.
• the density of the plastic bottle is appropriately selected depending on the polyester resin.
• plastic bottles produced by the production method of the present invention include dairy products, soft drinks, beverage container bottles such as alcoholic beverages, storage containers for seasonings such as soy sauce and edible oil, shampoos, rinses, etc. Detergent containers, cosmetic containers and the like.
• a manufacture example is a manufacture example of a resin composition
• an Example is a manufacture example of a plastic bottle using the obtained resin composition
• Comprising: The manufacture of a plastic bottle is a preform molding process, although it consists of three stages, a mouth crystallization process and a bottle molding process, each manufacturing process evaluated.
• Example 1 used the resin composition 1 obtained in Production Example 1, and Comparative Examples 1 to 4 used Comparative Resin Compositions 1 to 4 obtained in Comparative Production Examples 1 to 4, respectively. These results are shown in Table 1 below.
• Comparative resin composition 1 containing no crystal nucleating agent and no crystal nucleating agent was added to polyethylene terephthalate resin (CB-651 manufactured by Far East Boshoku Co., Ltd.).
• Comparative Production Example 2 A resin composition having a crystal nucleating agent (compound No. 1) concentration of 0.027%, prepared in the same manner as in Production Example 1, except that 10 parts by mass of the master batch was mixed with 100 parts by mass of the polyester resin. Comparative resin composition 2 was obtained.
• Preform molding process The resin compositions obtained in Production Example 1 and Comparative Production Examples 1 to 4 were each dried in a gear oven at 160 ° C. for 4 hours, and then injection molded (Nissei ASB Machine Co., Ltd .; ASB-50HT). A preform (outer diameter 25 mm, weight 23 g) was molded at a molding temperature of 280 ° C. injection temperature. The following evaluation was performed about the obtained preform.
• the molded preform was subjected to mouth crystallization using a mouth crystallization apparatus (apparatus: CM-2000 manufactured by Nissei ASB Machine Co., Ltd.). In the mouth crystallization, the mouth portion of the preform was heated at 160 to 180 ° C. for about 90 seconds to promote crystallization.
• the preform of the comparative resin composition 3 obtained in Comparative Production Example 3 was confirmed to be clouded and the preform could not be stretched by a blow molding machine, the preform of the comparative resin composition 3 was Partial crystallization was not performed. The following evaluation was performed on the mouth crystallization of the preform.
• Molding cycle The number of crystallization of the mouth per hour of the preform was counted.
• Crystallization temperature The plastic bottle obtained by the above method is cut out and finely cut, dried under reduced pressure at 150 ° C. for 5 hours, weighed 5 mg and filled into an aluminum pan, and a differential scanning calorimeter (device: The crystallization temperature was measured with a diamond manufactured by Perkin Elmer. In the measurement, when the temperature was raised to 300 ° C. at a rate of 10 ° C./min, held for 1 minute and then cooled to 50 ° C. at 10 ° C./min, the exothermic peak temperature was determined as the crystallization temperature.
• the plastic bottle produced without blending the crystal nucleating agent had a very slow molding cycle as compared with Example 1, although it had little effect on transparency and yellowness.
• Comparative Example 2 in the plastic bottle, when the crystal nucleating agent is blended in an amount exceeding 0.027 parts by mass and 0.025 parts by mass with respect to 100 parts by mass of the polyester resin, the appearance of the preform has a white haze. As a result, when blow-molded, a white turbidity was produced in the appearance, and a plastic bottle with impaired transparency was obtained.
• Example 1 On the other hand, from Example 1, it was confirmed that the plastic bottle produced by the production method of the present invention had a good appearance and shortened the molding cycle. And since Example 1 and Comparative Example 1 are compared and there is no difference in the density after blow molding, the plastic bottle produced by the production method of the present invention is almost in terms of crystallization of the polyester resin during blow molding. It was confirmed that there was no effect, the coloring of the molded product was suppressed, and the preform molding cycle was greatly improved.

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