JP5563282B2 - Method for producing crystal nucleating agent for polyester resin - Google Patents

Description

  The present invention relates to a method for producing a polyester resin crystal nucleating agent, and more specifically, a polyester resin crystal nuclei having a small particle diameter and capable of obtaining a crystal nucleating agent for polyester resin that is unlikely to cause secondary aggregation during storage. The present invention relates to a method for producing an agent.

  Polyester resins such as polyethylene terephthalate, polymethylene terephthalate, and polylactic acid are excellent in transparency, heat resistance, chemical resistance, mechanical properties, electrical properties, gas barrier properties, and cost performance. Especially, the main repeating unit is ethylene. Polyethylene terephthalate, which is terephthalate (hereinafter sometimes referred to as “PET resin”), is a bottle of carbonated beverages, juice, mineral water, etc., cosmetics, pharmaceutical containers, detergent / shampoo containers, toner for electrophotography, food, pharmaceuticals Widely used in packaging materials. However, although polyethylene terephthalate is a crystalline polymer, the range of molding conditions is extremely narrow and it is difficult to improve the molding cycle, and the use of molding materials is still limited.

  This drawback is derived from the crystallinity of the polyester resin, and it is known that the addition of a crystal nucleating agent increases the crystallization temperature of the polyester resin and improves the molding cycle.

  In Patent Document 1, the present inventors have provided an invention for promoting crystallization of a polyester resin composition using a sulfonamide compound metal salt as a crystal nucleating agent for a polyester resin, which cannot be achieved with a conventional crystal nucleating agent. We realized a molding cycle that did not exist.

  However, when the sulfonamide compound metal salt added to the polyester resin contains particles exceeding 250 μm, it may remain unmelted during melt-kneading with the polyester resin. When such a crystal nucleating agent is applied to a fiber material, for example, the fiber breaks when the fiber is stretched, or when it is applied to a film material, fish eyes appear on the film surface or the sheet is stretched uniformly. It may not be possible, or there may be holes in the film surface. Further, when the crystal nucleating agent is used in the molding of a bottle container or a sheet, there is a problem that the crystallization accelerating action of the polyester resin is too strong, and a part or the whole of the molded product is whitened to deteriorate the appearance.

  It has been found that this problem can be improved by uniformly dispersing the polyester resin crystal nucleating agent in the polyester resin. In order to uniformly disperse, for example, the above-mentioned problem can be solved by grinding until the volume average particle diameter is in a range of 0.5 to 50 μm and a mesh path of 250 μm.

JP 2007-327028 A

  However, when the above crystal nucleating agent is pulverized for a long time until the volume average particle size becomes 0.5 to 50 μm, the pulverized product is hardened and adhered to the tank (adhered), or pulverized by heat generated during pulverization. There was a problem that the product melted into a lump (fused) state and could hardly be recovered and could not be stably pulverized. In addition, there is a problem in that blocking occurs due to secondary aggregation of the pulverized product during transportation and warehouse storage.

  Accordingly, an object of the present invention is to produce a crystal nucleating agent for polyester resin that can solve the above-mentioned conventional problems, and that can provide a crystal nucleating agent for polyester resin that has a small particle size and is less likely to cause secondary aggregation during storage. It is to provide a method.

  As a result of intensive studies to solve the above problems, the present inventors have dried the crystal nucleating agent until the water content becomes a specific value or less, and pulverized using a pulverizer that does not use a pulverizing medium. As a result, the present inventors have found that the above problems can be solved, and have completed the present invention.

  That is, the method for producing a crystal nucleating agent for polyester resin of the present invention is a method for producing a crystal nucleating agent for polyester resin comprising a sulfonamide compound metal salt or a sulfonimide compound metal salt, wherein the crystal nucleating agent for polyester resin is Then, after drying until the water content becomes 8% by mass or less, pulverization is performed by a pulverizer without using a pulverizing medium.

  In the method for producing a crystal nucleating agent for polyester resin of the present invention, the pulverized polyester resin crystal nucleating agent has a volume average particle diameter in the range of 0.5 to 50 μm and a 250 μm mesh path of 90% by mass or more. It is preferable that

  Further, in the method for producing a crystal nucleating agent for polyester resin of the present invention, the crystal nucleating agent for polyester resin is a benzenesulfonamide metal salt, toluene-4-sulfonamide metal salt, N-phenyl-benzenesulfonamide metal salt, N-phenyl-4-methyl-benzenesulfonamide metal salt and 1,2-benzisothiazol-3 (2H) -one 1,1-dioxide metal salt are preferable. .

  Further, in the method for producing a crystal nucleating agent for polyester resin of the present invention, the crystal nucleating agent for polyester resin is benzenesulfonamide sodium salt, toluene-4-sulfonamide sodium salt, N-phenyl-benzenesulfonamide sodium salt, It is selected from the group consisting of N-phenyl-4-methyl-benzenesulfonamide sodium salt and 1,2-benzisothiazol-3 (2H) -one 1,1-dioxide sodium salt preferable.

  Further, in the method for producing a crystal nucleating agent for polyester resin according to the present invention, the pulverizer not using the pulverizing medium is a roll pulverizer, a high-speed rotational impact pulverizer, an airflow pulverizer, and a shear / grinding type. It is preferably selected from the group consisting of pulverizers.

  In the method for producing a crystal nucleating agent for polyester resin of the present invention, the recovered amount of the crystal nucleating agent for polyester resin after pulverization is preferably 90% or more.

  According to the present invention, there can be obtained a crystal nucleating agent for a polyester resin comprising a sulfonamide compound or a sulfonimide compound, which has a small particle diameter and hardly causes secondary aggregation during storage. .

The pulverization method of the present invention will be described in detail below.
The polyester resin crystal nucleating agent comprising a sulfonamide compound metal salt or a sulfonimide compound metal salt according to the present invention represents a metal salt of a compound having a sulfonamide skeleton or a sulfonimide skeleton. Examples of the compound having a sulfonamide skeleton or a sulfonimide skeleton include, for example, sulfonamide, methanesulfonamide, benzenesulfonamide, toluene-4-sulfonamide, 4-chlorobenzenesulfonamide, 4-aminobenzenesulfonamide, N-butyl- 4-methyl-benzenesulfonamide, N-phenyl-benzenesulfonamide, N-phenyl-methyl-benzenesulfonamide, 4-amino-N-pyridin-2-ylbenzenesulfonamide, 4-amino-N- (5- Methyl-thiazol-2-yl) -benzenesulfonamide, 4-amino-N-thiazol-2-yl-benzenesulfonamide, 4-amino-N- (5-methyl-isoxazol-3-yl) -benzenesulfonamide 4-amino-N- (2, -Dimethoxy-pyrimidin-4-yl) -benzenesulfonamide, 1,2-benzisothiazol-3 (2H) -one 1,1-dioxide, 4-amino-6-chloro-benzene-1,3-disulfonic acid Diamide, 6-ethoxy-benzothiazole-2-sulfonic acid amide, 5-dimethylamino-naphthalene-1-sulfonic acid amide, 4-sodiumoxy-benzenesulfonamide, N- (4-benzenesulfonylamino-phenyl) -benzene In the present invention, benzenesulfonamide, toluene-4-sulfonamide, N-phenyl-benzenesulfonamide, N-phenyl-4-methyl-benzenesulfonamide, 1,2-benzisothiazole -3 (2H) -one 1,1-dioxide metal salt It shall preferably used.

  The metal in the metal salt of the sulfonamide compound or sulfonimide compound is selected from lithium, potassium, sodium, magnesium, calcium, strontium, barium, titanium, manganese, iron, zinc, silicon, zirconium, yttrium, or barium. Among them, potassium, lithium, sodium, and calcium are preferable because they are excellent in the crystallization promoting effect of the polyester resin, and sodium is particularly preferable.

  In the present invention, a known dryer can be used as a method for drying the moisture content of the polyester resin crystal nucleating agent to 8% by mass or less. Examples of the dryer used in the present invention include a spray dryer, a vacuum freeze dryer, a vacuum dryer, a stationary shelf dryer, a mobile shelf dryer, a fluidized bed dryer, a rotary dryer, a stirring dryer, and the like. Is mentioned.

  The water content of the crystal nucleating agent for polyester resin is, using Rigaku Corporation Thermo Plus 2, under the condition of nitrogen (flow rate: 200 ml / min), sample: 5 mg, heating rate: 50 ° C./min, The weight loss when the temperature reaches 150 ° C. from room temperature is the moisture content contained in the measurement sample, and the ratio between the moisture content and the weight of the measurement sample is evaluated as the moisture content. In the present invention, the polyester resin What is necessary is just to dry the moisture content of the crystal nucleating agent for water to 8 mass% or less, Preferably drying of 5 mass% or less is preferable. When the water content exceeds 8% by mass, the pulverization time of the crystal nucleating agent for polyester resin by the pulverizer becomes long and the pulverization efficiency deteriorates, the pulverized products aggregate in the pulverization tank, or the pulverization tank There is a possibility that the pulverized product adheres to and hardens, or secondary agglomeration occurs after pulverization. Moreover, drying to less than 0.01% by mass is uneconomical, and it may be dried within a range of 0.01 to 8% by mass in the pulverization method of the present invention.

  In the method for producing a polyester resin crystal nucleating agent of the present invention, the polyester resin crystal nucleating agent is dried until the water content becomes 8% by mass or less, and then pulverized by a pulverizer without using a pulverizing medium. In the present invention, the grinding medium refers to a solid material, for example, non-metal such as glass, meno, silicon nitride, zirconia, steatite, etc .; metal such as alumina, titania, etc .; tungsten carbide, chrome Examples thereof include those made of alloys such as steel and stainless steel. The form is not limited, and examples thereof include beads and balls.

  The pulverizer used in the present invention is not particularly limited as long as the pulverizing medium is not used, and pulverization using a roll type, a high-speed rotational impact type, an airflow type, or a shearing / grinding type pulverization method. These may be a combination of these pulverization methods, or may be a combination of pulverization devices, and a system incorporating a classification mechanism can also be employed.

  Examples of the roll pulverizer include a roll rotating mill in which pulverization is performed between rotating rolls, and a roller rolling mill in which a roller rolls in a table or container.

  Examples of the above high-speed rotational impact type pulverizer include those that collide a sample with a high-speed rotating rotor and achieve miniaturization by the impact force. For example, a fixed or swing type impactor is attached to the rotor. Hammer mill type hammer type, pin mill type rotating disk type with a pin and impact head attached to a rotating disk, axial flow type that pulverizes while the sample is conveyed in the shaft direction, and refinement of particles in a narrow annular part An annular type etc. are mentioned.

  The airflow crusher (jet mill) is a type that uses the kinetic energy of a high-speed gas-fluid to accelerate and collide the sample and crush it. In addition, there may be mentioned those which are mainly pulverized mainly by making particles by friction between particles.

  Examples of the shearing / grinding type pulverizer include a grinding type pulverizer using a shear frictional force under a compressive force.

  In addition, as a medium type pulverizer using a pulverizing medium, a kinetic force is exerted on the medium by a container-driven mill that drives an internal pulverizing medium and a stirring mechanism inside the container when the container rotates or vibrates. A medium stirring mill that gives Examples of the container-driven mill include a rolling ball mill such as a ball mill, a vibration mill, a centrifugal mill, a planetary mill, a high swing mill, and the like. Examples include a tank type, a distribution pipe type, and an annular type.

  In the present invention, the polyester resin crystal nucleating agent preferably has a volume average particle size in the range of 0.5 to 50 μm, more preferably 1 μm to 30 μm by a pulverizer that does not use the pulverization medium, And it grind | pulverizes until a 250 micrometer mesh pass becomes 90 mass% or more preferably, More preferably, it is 95 mass% or more.

  If the volume average particle size is less than 0.5 μm, energy consumption required for pulverization increases, which is uneconomical. If it exceeds 50 μm, the pulverized product is not dispersed in the polyester resin when molded into the polyester resin. In some cases, the appearance of the molded product may be impaired. If the 250 μm mesh path is less than 90% by mass, coarse particles may remain unmelted in the resin during melt kneading with the polyester resin, which may adversely affect the appearance and physical properties of the molded product.

  Further, in the pulverization method of the present invention, the recovery rate of the pulverized product of the polyester resin crystal nucleating agent is preferably 90% or more, more preferably 95% or more. If it is less than 90%, it may accumulate in the pulverizing tank of the pulverizer and hinder pulverization.

  In the present invention, the pulverized product of the crystal nucleating agent for polyester resin is preferably dried until the water content becomes 1% by mass or less. When a water content exceeding 1% by mass is blended with a polyester resin and molded, bubbles may be generated to impair the appearance of the molded product. Moreover, it is uneconomic to dry to less than 0.01 mass%. As the drying method, a known drying method can be used in the same manner as described above.

  When the pulverized products are agglomerated by weak interparticle attraction, the agglomerates are preferably used after being crushed. As a device for crushing, a known crushing treatment device can be used, and examples thereof include a jet mill and a Henschel mixer.

As the polyester resin according to the present invention, a normal thermoplastic polyester resin is used and should not be particularly limited. For example, polyoxyalkylene terephthalate such as polyethylene terephthalate, polybutylene terephthalate, polycyclohexane dimethylene terephthalate, aromatic polyester such as polyalkylene naphthalate such as polyethylene naphthalate and polybutylene naphthalate; polyester component and other acid components and / Or glycol components (eg, acid components such as isophthalic acid, adipic acid, sebacic acid, glutaric acid, diphenylmethane dicarboxylic acid, dimer acid, glycol components such as hexamethylene glycol, bisphenol A, neopentyl glycol alkylene oxide adduct) Polyether ester resin copolymerized with polyhydroxybutyrate, polycaprolactone, polybutylene succinate, polyethylene succinate Degradable aliphatic polyester such as polylactic acid resin, polymalic acid, polyglycolic acid, polydioxanone, poly (2-oxetanone); aromatic polyester / polyether block copolymer, aromatic polyester / polylactone block copolymer, poly A broadly defined polyester resin such as arylate is also used.
Among them, one or more polyester resins selected from the group consisting of polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate and polylactic acid are preferably used, and in particular, polyethylene terephthalate is more preferable because it is excellent in transparency and inexpensive. .

  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 copolymer of polybutylene terephthalate and polytetramethylene glycol). In particular, those having a melting point of 200 ° C. to 300 ° C. are preferably used because they exhibit heat resistance.

  The addition amount of the crystal nucleating agent for polyester resin with respect to 100 parts by mass of the polyester resin is 0.001 to 1 part by mass, and more preferably 0.005 to 0.5 part by mass. When the amount is less than 0.001 part by mass, the effect as a crystal nucleating agent is low. When the amount is more than 1 part by mass, the dispersibility in the polyester resin is lowered, which may adversely affect the appearance and physical properties of the molded product. .

The polyester resin containing the polyester resin crystal nucleating agent may further contain other usual additives as required. As a method for blending other additives, there is a method in which other additives are mixed with a polyester resin in a blending amount according to the purpose, and melt-kneaded in a molding machine such as an extruder, and then granulated and molded. Other additives may be blended together with the crystal nucleating agent for the polyester resin, and after molding the polyester resin blended with the crystal nucleating agent for the polyester resin, other additives are added to the molding process. You may shape | mold using a machine.
Examples of other additives include phenolic antioxidants, phosphorus antioxidants, ultraviolet absorbers, hindered amine compounds, heavy metal deactivators, other crystal nucleating agents other than the crystal nucleating agent used in the present invention, difficulty Examples include flame retardants, metal soaps, hydrotalcite, fillers, lubricants, antistatic agents, pigments, dyes, and plasticizers.

Examples of the phenol-based antioxidant 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- (4-hydroxy-3-tert-butylphenyl) butyric acid] glycol ester, 4,4′-butylidenebis (2,6-ditert-butylphenol), 4,4′-butylidenebis (6-tert-butyl- 3-methylphenol), 2,2′-ethylidenebis (4,6-ditert-butylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, bis [2-tert-butyl-4-methyl-6- (2-hydroxy-3-tert-butyl-5-methylbenzyl) phenyl] terephthalate, 1,3,5-tris (2,6-dimethyl-3-hydroxy -4-tert-butylbenzyl) isocyanurate, 1,3,5-tris (3,5-ditert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (3 , 5-Ditert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, 1,3,5-tris [(3,5-ditert-butyl-4-hydroxyphenyl) propionyloxyethyl] Isocyanurate, tetrakis [methylene-3- (3 ′, 5′-ditert-butyl-4′-hydroxyphenyl) propionate] methane, 2-tert-butyl-4-methyl-6- (2-acroyloxy- 3-tert-butyl-5-methylbenzyl) phenol, 3,9-bis [2- (3-tert-butyl-4-hydroxy-5-methylhydrocinnamoyloxy) -1,1-dimethylethyl] -2 , 4,8,10-tetraoxaspiro [5.5] undecane, triethylene glycol bis [β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate ], And the like.
The usage-amount of the said phenolic antioxidant is 0.001-10 mass parts with respect to 100 mass parts of said polyester resins, More preferably, it is 0.01-5 mass parts.

Examples of the phosphorus antioxidant include triphenyl phosphite, trisnonylphenyl phosphite, tris (2,4-ditert-butylphenyl) phosphite, tris (2,4-ditert-butyl-5- Methylphenyl) phosphite, tris [2-tert-butyl-4- (3-tert-butyl-4-hydroxy-5-methylphenylthio) -5-methylphenyl] phosphite, tridecyl phosphite, octyldiphenylphos Phyto, di (decyl) monophenyl phosphite, di (tridecyl) pentaerythritol diphosphite, di (nonylphenyl) pentaerythritol diphosphite, bis (2,4-ditert-butylphenyl) pentaerythritol diphosphite, Bis (2,6-ditert-butyl-4-methylphenyl) pentaeryth Tall diphosphite, bis (2,4,6-tritert-butylphenyl) pentaerythritol diphosphite, bis (2,4-dicumylphenyl) pentaerythritol diphosphite, tetra (tridecyl) isopropylidenediphenol di Phosphite, tetra (tridecyl) -4,4′-n-butylidenebis (2-tert-butyl-5-methylphenol) diphosphite, hexa (tridecyl) -1,1,3-tris (2-methyl-4-hydroxy) -5-tert-butylphenyl) butane triphosphite, tetrakis (2,4-ditert-butylphenyl) biphenylene diphosphonite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide 2,2′-methylenebis (4,6-tert-butylphenyl) -2-e Tylhexyl phosphite, 2,2′-methylenebis (4,6-tert-butylphenyl) -octadecyl phosphite, 2,2′-ethylidenebis (4,6-ditert-butylphenyl) fluorophosphite, tris (2 -[(2,4,8,10-tetrakis tert-butyldibenzo [d, f] [1,3,2] dioxaphosphin-6-yl) oxy] ethyl) amine, 2-ethyl-2- Examples thereof include phosphites of butylpropylene glycol and 2,4,6-tritert-butylphenol.
The usage-amount of the said phosphorus antioxidant is 0.001-10 mass parts with respect to 100 mass parts of said polyester resins, More preferably, it is 0.01-5 mass parts.

Examples of the ultraviolet absorber 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-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-tertiary Octyl-6-benzotriazolylphenol), 2- (2-hydroxy-3-tert-butyl-5-carboxyphenyl) benzotriazole polyethylene glycol ester, 2- [2-hydroxy-3- (2-acryloyloxy) Ethyl) -5-methylphenyl] benzotriazole, 2- [2-hydroxy-3- (2-methacryloyloxyethyl) -5-tert-butylphenyl] benzotriazole, 2- [2-hydroxy-3- (2- Methacryloyloxyethyl) -5-tert-octylphenyl] benzotriazole, 2- [2-hydroxy-3- (2-methacryloyloxyethyl) -5-tert-butylphenyl] -5-chlorobenzotriazole, 2- [2 -Hydroxy-5- (2-methacryloyloxyethyl) phenyl] benzo Triazole, 2- [2-hydroxy-3-tert-butyl-5- (2-methacryloyloxyethyl) phenyl] benzotriazole, 2- [2-hydroxy-3-tert-amyl-5- (2-methacryloyloxyethyl) ) Phenyl] benzotriazole, 2- [2-hydroxy-3-tert-butyl-5- (3-methacryloyloxypropyl) phenyl] -5-chlorobenzotriazole, 2- [2-hydroxy-4- (2-methacryloyl) Oxymethyl) phenyl] benzotriazole, 2- [2-hydroxy-4- (3-methacryloyloxy-2-hydroxypropyl) phenyl] benzotriazole, 2- [2-hydroxy-4- (3-methacryloyloxypropyl) phenyl ] 2- (2-hydroxyphenyl) such as benzotriazole Benzotriazoles; 2- (2-hydroxy-4-methoxyphenyl) -4,6-diphenyl-1,3,5-triazine, 2- (2-hydroxy-4-hexyloxyphenyl) -4,6-diphenyl -1,3,5-triazine, 2- (2-hydroxy-4-octoxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2- Hydroxy-4- (3-C12-13 mixed alkoxy-2-hydroxypropoxy) phenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2-hydroxy- 4- (2-acryloyloxyethoxy) phenyl] -4,6-bis (4-methylphenyl) -1,3,5-triazine, 2- (2,4-dihydroxy-3-allylphenyl) 4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2,4,6-tris (2-hydroxy-3-methyl-4-hexyloxyphenyl) -1,3,5 2- (2-hydroxyphenyl) -4,6-diaryl-1,3,5-triazines such as triazine; phenyl salicylate, resorcinol monobenzoate, 2,4-ditert-butylphenyl-3,5-di Tert-butyl-4-hydroxybenzoate, octyl (3,5-ditert-butyl-4-hydroxy) benzoate, dodecyl (3,5-ditert-butyl-4-hydroxy) benzoate, tetradecyl (3,5-di Tert-butyl-4-hydroxy) benzoate, hexadecyl (3,5-ditert-butyl-4-hydroxy) benzoate, octadecyl (3,5-ditert-butyl) Benzoates such as til-4-hydroxy) benzoate and behenyl (3,5-ditert-butyl-4-hydroxy) benzoate; 2-ethyl-2′-ethoxyoxanilide, 2-ethoxy-4′-dodecyloxy Substituted oxanilides such as zanilides; cyanoacrylates such as ethyl-α-cyano-β, β-diphenyl acrylate and methyl-2-cyano-3-methyl-3- (p-methoxyphenyl) acrylate; various metal salts Or metal chelates, especially nickel, chromium salts, or chelates.
The usage-amount of the said ultraviolet absorber is 0.001-5 mass parts with respect to 100 mass parts of said polyester resins, More preferably, it is 0.005-0.5 mass part.

Examples of the hindered amine light stabilizer include 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl stearate, 2,2, 6,6-tetramethyl-4-piperidylbenzoate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1 , 2,3,4-butanetetracarboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, bis (2,2, 6,6-tetramethyl-4-piperidyl) di (tridecyl) -1,2,3,4-butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4 Piperidyl) .di (tridecyl) -1,2,3,4-butanetetracarboxylate, bis (1,2,2,4,4-pentamethyl-4-piperidyl) -2-butyl-2- (3,5 -Di-tert-butyl-4-hydroxybenzyl) malonate, 1- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-piperidinol / diethyl succinate polycondensate, 1,6- Bis (2,2,6,6-tetramethyl-4-piperidylamino) hexane / 2,4-dichloro-6-morpholino-s-triazine polycondensate, 1,6-bis (2,2,6,6 -Tetramethyl-4-piperidylamino) hexane / 2,4-dichloro-6-tert-octylamino-s-triazine polycondensate, 1,5,8,12-tetrakis [2,4-bis (N-butyl) -N- (2,2, , 6-tetramethyl-4-piperidyl) amino) -s-triazin-6-yl] -1,5,8,12-tetraazadodecane, 1,5,8,12-tetrakis [2,4-bis ( N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino) -s-triazin-6-yl] -1,5,8-12-tetraazadodecane, 1,6 , 11-tris [2,4-bis (N-butyl-N- (2,2,6,6-tetramethyl-4-piperidyl) amino) -s-triazin-6-yl] aminoundecane, 1,6 , 11-tris [2,4-bis (N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino) -s-triazin-6-yl] aminoundecane, bis { 4- (1-octyloxy-2,2,6,6-tetra Methyl) piperidyl} decanedionate, bis {4- (2,2,6,6-tetramethyl-1-undecyloxy) piperidyl) carbonate, TINUVIN NOR 371 and the like.
The usage-amount of the said hindered amine light stabilizer is 0.001-5 mass parts with respect to 100 mass parts of said polyester resins, More preferably, it is 0.005-0.5 mass part.

Examples of other crystal nucleating agents include, for example, simple substances such as carbon black, graphite, zinc powder, and aluminum powder; metal oxides such as zinc oxide, magnesium oxide, alumina, hematite, and magnetite; talc, asbestos, kaolin, and montmorillonite. Clays, ores such as clay and pyrophyllite, sulfates such as calcium sulfate and barium sulfate; inorganic phosphates such as calcium phosphate; metal salts of aromatic oxysulfonic acid, magnesium salts of organic phosphorus compounds, zinc of organic phosphorus compounds Organic phosphates such as salts; inorganic silicates such as calcium silicate salt and magnesium silicate salt; sodium monocarboxylate, lithium monocarboxylate, barium monocarboxylate, magnesium monocarboxylate, calcium monocarboxylate , Sodium stearate, Sodium ntannate, sodium benzoate, potassium benzoate, calcium benzoate, 4-tert-butylaluminum benzoate, sodium adipate and disodium bicyclo [2.2.1] heptane-2,3-dicarboxylate, Carboxylic acid metal salts such as sodium carbonate and magnesium carbonate; sodium bis (4-tert-butylphenyl) phosphate, sodium-2,2′-methylenebis (4,6-ditert-butylphenyl) phosphate and lithium-2,2 Phosphate metal salts such as' -methylenebis (4,6-ditert-butylphenyl) phosphate; dibenzylidene sorbitol, bis (methylbenzylidene) sorbitol, bis (p-ethylbenzylidene) sorbitol, and bis (dimethylbenzylidene) sorbitol Multivalent such as Alcohol derivatives; N, N ′, N ″ -tris [2-methylcyclohexyl] -1,2,3-propanetricarboxamide, N, N ′, N ″ -tricyclohexyl-1,3,5-benzenetricarboximide Amide compounds such as N, N′-dicyclohexyl-naphthalenedicarboxamide, 1,3,5-tris (2,2-dimethylpropionylamino) benzene; polycaprolactone, polyglycol, polyolefin, nylon 6, polytetrafluoroethylene powder And high-melting point PET, polymer materials such as alkali metal salts of polyester oligomers, and the like.
The amount of the other crystal nucleating agent used is such that the total amount with the crystal nucleating agent used in the present invention is 0.001 to 1 part by mass with respect to 100 parts by mass of the polyester resin.

Examples of the flame retardant include aromatic phosphoric acid such as triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, cresyl-2,6-xylenyl phosphate, and resorcinol bis (diphenyl phosphate). Phosphonates such as esters, divinyl phenylphosphonate, diallyl phenylphosphonate and phenylphosphonic acid (1-butenyl), phenyl diphenylphosphinate, methyl diphenylphosphinate, 9,10-dihydro-9-oxa-10-phospha Phosphonic acid esters such as phenanthrene-10-oxide derivatives, phosphazene compounds such as bis (2-allylphenoxy) phosphazene and dicresyl phosphazene, melamine phosphate, melamine pyrophosphate, Melamine phosphate, melam polyphosphate, ammonium polyphosphate, phosphorus-containing vinylbenzyl compounds and phosphorus-based flame retardants such as red phosphorus, metal hydroxides such as magnesium hydroxide and aluminum hydroxide, brominated bisphenol A type epoxy resin, bromine Phenol novolac epoxy resin, hexabromobenzene, pentabromotoluene, ethylenebis (pentabromophenyl), ethylenebistetrabromophthalimide, 1,2-dibromo-4- (1,2-dibromoethyl) cyclohexane, tetrabromocyclo Octane, hexabromocyclododecane, bis (tribromophenoxy) ethane, brominated polyphenylene ether, brominated polystyrene and 2,4,6-tris (tribromophenoxy) -1,3,5-triazine, tribromophenyl Reimido, tribromophenyl acrylate, tribromophenyl methacrylate, tetrabromobisphenol A type dimethacrylate, pentabromobenzyl acrylate, and include brominated flame retardants such as brominated styrene and the like.
The usage-amount of the said flame retardant is 1-70 mass parts with respect to 100 mass parts of said polyester resins, More preferably, it is 10-30 mass parts.

  The molding method of the polyester resin composition of the present invention is not particularly limited, and known molding methods such as extrusion molding, injection molding, hollow molding, blow, film, and sheet can be used. The temperature condition of the extruder is preferably such that the screw part temperature is within the melting point of the resin plus 50 ° C. If the screw temperature is too low, a short circuit will occur and the molding will become unstable or easily overloaded, and if the molding temperature is too high, the resin will be thermally decomposed and the physical properties of the resulting molded product will be reduced or colored. It is not preferable because it may cause

  After the molding of the polyester resin composition of the present invention, the molded product may be annealed. The annealing treatment is a heat treatment of the molded product within a range of 1 second to 2 minutes at a temperature not lower than the glass transition temperature of the polyester resin and not higher than the melting point. Although the crystallinity of the molded product can be improved in a short time of less than 1 second, 1 second or more is preferable in order to keep the annealing effect constant for quality control, and the crystallization of the molded product proceeds after 2 minutes. Too much whitening and transparency may be impaired.

When the heating temperature of the annealing treatment is lower than the glass transition temperature, the crystallinity of the molded product is hardly improved, and when the temperature is higher than the melting point, the molded product is melted and the appearance cannot be maintained. A more preferable temperature is in the range of glass transition temperature to glass transition temperature + 150 ° C., and particularly preferably in the range of glass transition temperature + 50 ° C. to glass transition temperature + 120 ° C.
The heating method is not particularly limited, and a method that can uniformly heat the entire molded product is preferable, but a part or a plurality of parts may be heated. Moreover, as long as the temperature does not impair the appearance of the molded product, the annealing treatment may be performed a plurality of times at different temperatures.

  Applications of the polyester resin composition of the present invention include bottles, packaging materials, beverage bottles, food containers, cosmetics, medical containers, food packaging materials, wrapping materials, sheets and films, and protective sheets for electrical appliances. It can be used for packaging materials for transportation, protective films for electronic materials, daily goods, toys and the like.

  Hereinafter, the present invention will be described more specifically based on examples. However, the present invention is not limited by the following examples.

The pulverizers and pulverization conditions in Examples and Comparative Examples are as shown in Table 1 below. The pulverization methods of Examples 1 to 8 for the crystal nucleating agent for each polyester resin are shown in Table 2 below, and the pulverization methods of Comparative Examples 1 to 8 are shown in Table 3 below.
These pulverization results are shown in Table 4 below. The water content, the particle size of the obtained pulverized product, the mesh pass of 250 μm and the recovery rate were evaluated according to the following.

(Method for evaluating moisture content)
The moisture content was calculated based on the following formula by measuring the moisture content of the crystal nucleating agent for a polyester resin before pulverization using Thermoplus 2 / (TG-DTA series) manufactured by Rigaku Corporation. The weight loss when the temperature reached 150 ° C. from room temperature under the conditions of nitrogen atmosphere (flow rate: 200 ml / min), measurement sample: 5 mg, and heating rate: 50 ° C./min was defined as the amount of water contained in the measurement sample. .
Moisture content (%) = (water content) / (measurement sample weight) × 100

(Evaluation method of particle size)
The particle diameter is measured with a laser diffraction / scattering particle size distribution meter (Microtrack particle size distribution measuring device MT3300; manufactured by Nikkiso Co., Ltd.) for a pulverized product of a crystal nucleating agent for polyester resin. The particle size distribution (volume distribution) was measured under a dry method, and the 50% average particle size (50% D) and 90% particle size (90% D) were determined from the obtained particle size distribution.

  The 50% average particle diameter represents a volume weighted average obtained on the assumption that the sphere has a diameter corresponding to the measured particle diameter, and the 90% particle diameter represents the particle diameter in the particle size distribution histogram. Accumulation was performed from the smallest particle size, and the initial particle diameter was 90%.

(250 μm mesh path)
The 250 μm mesh pass represents the proportion of the pulverized product that has passed through the 250 μm mesh pass. When a mesh pass of 90% by mass or more was obtained with respect to the input amount of the sample, it was evaluated as ◯, and when it was not obtained, it was evaluated as x. When the pulverized product was fixed in the pulverizing tank during pulverization, it was evaluated as x.

(Load resistance evaluation method)
The load resistance was examined to determine the possibility of blocking due to secondary agglomeration when the pulverized polyester nucleating agent filled in the bag was transported in a loaded state. . As a study method, an aluminum bag is filled with a pulverized product of a crystal nucleating agent for polyester resin, sealed so as not to contain air, and a load of 50 g / cm ² is applied to the bag in a constant temperature oven at 50 ° C. And left to stand.
When blocking occurred after one month, it was evaluated as x, and when it was not blocked, it was evaluated as ◯.

(Recovery rate)
The recovery rate represents the ratio of the pulverized product recovered with respect to the raw material. When the recovery rate was 90% or more, it was represented by ◯, and when the recovery rate was less than 90%, it was represented by ×.

(Crushing equipment and grinding conditions)

  About the pulverized product obtained in Examples 1 to 8 and Comparative Examples 1 to 8, the particle size, 250 μm mesh pass, load resistance, and recovery rate of the pulverized product were evaluated. These results are shown in Table 4 below.

According to Comparative Examples 1 to 5 in Table 4 above, when using a media pulverizer that pulverizes using a pulverizing medium, the pulverized product is stuck in the tank and hardly recovered, and the 250 μm mesh pass is also extremely small. It was slight. Moreover, even when it was a case where it grind | pulverized with the grinder which does not use a grinding | pulverization medium from Comparative Examples 6-8, when the moisture content was high, it was easy to secondary-aggregate and it was confirmed that it is blocking in the load test.
On the other hand, from Examples 1 to 8, the pulverization method of the present invention is stable within a desired particle diameter range by a method of pulverizing with a pulverizer having a water content of 8% by mass or less and not using a pulverization medium. It was confirmed that it could be crushed.

(Reference example)
The pulverized product obtained in Example 2 above was dried with a vacuum dryer (120 ° C. × 5 hours), and a water content of 0.3% was obtained as a polyethylene terephthalate resin (TR-8550 manufactured by Teijin Chemicals Ltd.). 0.3 parts by mass with respect to 100 parts by mass, mixed well, and granulated with a twin screw extruder (equipment: TEX28V manufactured by Nippon Steel Works, cylinder temperature: 270 ° C., screw speed: 200 rpm). However, pellets could be obtained without problems.
Next, when the pulverized product obtained in Example 2 above was granulated with a twin-screw extruder in the same manner as described above without drying under reduced pressure and with a moisture content of 2.1%, the strands foamed in the middle. It was cut and it was difficult to obtain pellets. As mentioned above, when adding to a polyester resin composition, it confirmed that it was preferable to dry and use a pulverized product until a moisture content became 1 mass% or less.

Claims (6)

A method for producing a crystal nucleating agent for polyester resin comprising a sulfonamide compound metal salt or a sulfonimide compound metal salt, wherein the crystal nucleating agent for polyester resin is dried until the water content is 8% by mass or less, and then a grinding medium method for producing a poly an ester resin for crystal nucleating agent characterized by grinding in grinder using no. Within a volume average particle diameter 0.5~50μm of the polyester resin for the crystal nucleating agent after the pulverization, and, 250 [mu] m mesh pass is 90 wt% or more of claim 1 wherein the poly an ester resin for crystal nuclei Manufacturing method. The crystal nucleating agent for polyester resin is a benzenesulfonamide metal salt, toluene-4-sulfonamide metal salt, N-phenyl-benzenesulfonamide metal salt, N-phenyl-4-methyl-benzenesulfonamide metal salt, and 1,2-benzisothiazol -3 (2H) - one 1,1-dioxide poly an ester manufacturing method for resin nucleating agent according to claim 1 or 2 wherein is selected from the group consisting of a metal salt. The crystal nucleating agent for polyester resin is benzenesulfonamide sodium salt, toluene-4-sulfonamide sodium salt, N-phenyl-benzenesulfonamide sodium salt, N-phenyl-4-methyl-benzenesulfonamide sodium salt, and 1,2-benzisothiazol -3 (2H) - method of manufacturing one 1,1-dioxide sodium are those selected from the group consisting of a salt according to claim 1 or 2 wherein the poly an ester resin for crystal nucleating agent . The pulverizer that does not use the pulverizing medium is selected from the group consisting of a roll pulverizer, a high-speed rotary impact pulverizer, an airflow pulverizer, and a shear / grinding pulverizer . poly an ester manufacturing method for resin nucleating agent according to any one claim of 4. Method for producing a poly an ester resin for crystal nucleating agent according to any one of claims 1 to 5 recovery of poly an ester resin for crystal nucleating agent after the pulverization is 90% or more.