JP2012116994A - Polyester resin composition and molded body of the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyester resin composition having improved physical properties, and a molded body of the same.SOLUTION: The polyester resin composition contains (A) a polyester resin and (B) a terminally modified polyethylene terephthalate, wherein (B) the terminally modified polyethylene terephthalate is a polyethylene terephthalate whose terminal is modified with a group represented by general formula (1) or with a group represented by general formula (1) and a metal carboxylate. In formula, X represents a direct bond or a 1-12C alkylene group.

Description

  The present invention relates to a polyester resin composition and a molded body thereof, and more particularly to a polyester resin composition and a molded body thereof improved in physical properties by improving a crystal nucleating agent to be added.

  Known polyester resins obtained by polycondensation of polycarboxylic acid and polyalcohol include polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, and polybutylene terephthalate. In particular, polyethylene terephthalate is a resin excellent in transparency, heat resistance, chemical resistance, hygiene, dyeability and economy, and is used for beverage containers such as fibers, films, carbonated drinks, juices, mineral water, etc. Bottles), cosmetic / medical products containers, detergent / shampoo containers, electrophotographic toners, food packaging materials, pharmaceutical packaging materials, packaging materials such as wraps, and the like.

  However, although polyethylene terephthalate is a crystalline resin, the crystallization rate is extremely slow, so the range of molding conditions is very narrow and it is difficult to improve the processing cycle. limited. Moreover, since the heat deformation temperature of the molded product obtained by molding is low, there is a problem that the use temperature is limited.

  As a method for improving the crystallization rate, it is known to add a crystal nucleating agent, and compounds such as silicon nitride, sodium benzoate, aromatic phosphate metal salt, dibenzylidene sorbitol are known. .

  In addition, Patent Document 1 discloses, as a crystallization accelerator, sodium montanate and stearic acid in a polyester molding material for tableware containing an inorganic filler with respect to two resins of polyethylene terephthalate and polybutylene terephthalate. Sodium, calcium montanate and calcium stearate have been proposed.

  Patent Documents 2 and 3 propose a metal salt of a sulfonamide compound as a crystal nucleating agent for a polyester resin.

JP 2001-200168 A JP 2007-327028 A International Publication No. 2008/038465

  However, the physical property improvement effect by the conventionally known crystal nucleating agent described in Patent Document 1 is still insufficient, and the development of a new crystal nucleating agent has been demanded. In addition, when the metal salt of the sulfonamide compound described in Patent Document 2 and Patent Document 3 is added to a polyester resin and molded, the dispersibility of the sulfonamide compound in the resin is poor, and the molded product obtained by molding processing There was a problem that some of them became cloudy.

  Therefore, an object of the present invention is to provide a polyester resin composition that has solved the above-described problems and improved physical properties, and a molded product thereof.

  As a result of repeated investigations in view of the above-described present situation, the present inventors have found that the above-described problems can be solved by using terminal-modified polyethylene terephthalate having a specific structure introduced at the terminal of polyethylene terephthalate as a crystal nucleating agent. The present invention has been completed.

（式中、Ｘは、直接結合又は炭素原子数１〜１２のアルキレン基を表す。） That is, the polyester resin composition of the present invention is a polyester resin composition containing (A) a polyester resin and (B) a terminal-modified polyethylene terephthalate, and the (B) terminal-modified polyethylene terephthalate has the following general formula: A polyester resin composition characterized by being a group represented by (1), or a polyethylene terephthalate having a terminal modified with a group represented by the following general formula (1) and a carboxylic acid metal salt.

(In the formula, X represents a direct bond or an alkylene group having 1 to 12 carbon atoms.)

  The polyester resin composition of the present invention is based on a total of 100 parts by mass of the (A) polyester resin and the balance obtained by removing the group represented by the general formula (1) from the (B) terminal-modified polyethylene terephthalate. The content of the group represented by the general formula (1) is preferably 0.001 to 1 part by mass.

  In the polyester resin composition of the present invention, the (A) polyester resin is one or more polyesters selected from the group consisting of polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate, polyethylene naphthalate, and polybutylene naphthalate. A resin is preferred.

  In the polyester resin composition of the present invention, the metal carboxylate is preferably a sodium carboxylate.

  The molded body of the present invention is obtained by molding the above-described polyester resin composition.

  The sheet | seat of this invention is a sheet | seat formed by sheet-molding said polyester resin composition, Comprising: The annealing process is not performed, It is characterized by the above-mentioned.

  According to the present invention, a polyester resin composition having improved physical properties and a molded product thereof can be provided.

It is an X-ray photoelectron spectrum of polyethylene terephthalate (PET) not containing a nucleating agent. 1 is an X-ray photoelectron spectroscopy spectrum of PET containing 1% of 1,2-benzisothiazol-3 (2H) -one 1,1-dioxide sodium salt. 1 is an X-ray photoelectron spectroscopy spectrum of PET containing 3% 1,2-benzisothiazol-3 (2H) -one 1,1-dioxide sodium salt. 1 is an X-ray photoelectron spectroscopy spectrum of PET containing 5% of 1,2-benzisothiazol-3 (2H) -one 1,1-dioxide sodium salt. 1 is an X-ray photoelectron spectrum of 1,2-benzisothiazol-3 (2H) -one 1,1-dioxide sodium salt. 2 is an X-ray photoelectron spectrum of N-ethyl alcohol-1,2-benzisothiazol-3 (2H) -one 1,1-dioxide.

[(A) Polyester resin]
The (A) polyester resin used in the present invention is a polymer linked by an ester bond and synthesized from a polyvalent carboxylic acid monomer and a polyhydric alcohol component. A polyester resin having an aromatic dicarboxylic acid or an alkyl ester thereof as a main acid component and ethylene glycol as a main glycol component is preferable. In the present invention, examples of the aromatic dicarboxylic acid or its alkyl ester include terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid, diphenyldicarboxylic acid, and alkyl esters thereof. Moreover, you may contain another aromatic dicarboxylic acid group like those halogenated equivalents. Among them, terephthalic acid or dimethyl terephthalic acid is preferably used, and usually 75 mol% or more, preferably 80 mol% or more, and most preferably 90 mol% or more is used in the acid component. These acid components may be used alone or in combination of two or more.

  In addition to the above compounds, aliphatic dicarboxylic acids such as adipic acid, sebacic acid, succinic acid, oxalic acid, or alkyl esters thereof can be used as the copolymerization component. Furthermore, a trifunctional or higher functional carboxylic acid such as trimellitic acid or an acid anhydride such as trimellitic anhydride can be used in a small amount. Examples of the alkyl esters of aromatic dicarboxylic acids include methyl esters as main utilization compounds, but ethyl esters, propyl esters, butyl esters and the like may be used alone or in combination of two or more. Well, it can be arbitrarily selected according to the purpose.

  In the present invention, glycol components other than ethylene glycol include propylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, decamethylene glycol, cyclohexanedimethanol, poly (oxy) ethylene glycol, poly One kind of alkylene glycol such as tetramethylene glycol or polymethylene glycol may be used, or two or more kinds may be used in combination, and can be arbitrarily selected according to the purpose. Furthermore, a small amount of a polyhydric alcohol component such as glycerin may be used, and a small amount of an epoxy compound may be used.

  The proportion of ethylene glycol in the glycol component is preferably 75 mol% or more, more preferably 80 mol% or more, and particularly preferably 90 mol% or more.

  Examples of suitable polyester resins include, for example, polyalkylene terephthalates such as polyethylene terephthalate, polybutylene terephthalate, polycyclohexanedimethylene terephthalate, and aromatic polyesters such as polyalkylene naphthalates such as polyethylene naphthalate and polybutylene naphthalate. Can be mentioned.

  The polyester resin according to the present invention may be a copolymer or a modified body of a plurality of polyester resins, or may be a polymer alloy of the above-described suitable polyester resin and the following other resins. The polymer alloy here refers to a polymer multi-component system, which may be a block polymer by copolymerization or a polymer blend by mixing.

Examples of the other resins include polyester components and other acid components and / or glycol components (for example, isophthalic acid, adipic acid, sebacic acid, glutaric acid, diphenylmethane dicarboxylic acid, dimer acid acid components, hexamethylene glycol, etc. , Bisphenol A, a glycol component such as neopentyl glycol alkylene oxide adduct), a polyetherester resin; polyhydroxybutyrate, polycaprolactone, polybutylene succinate, polyethylene succinate, polylactic acid resin, polymalic acid, Degradable aliphatic polyesters such as polyglycolic acid, polydioxanone, poly (2-oxetanone); aromatic polyester / polyether block copolymer, aromatic polyester / polylactone block copolymer, Broad polyester resins, such as arylate also be used.
In the present invention, those having a heat-resistant characteristic with a melting point of 200 ° C. to 300 ° C. are particularly preferably used.

（式中、Ｘは、直接結合又は炭素原子数１〜１２のアルキレン基を表す。） [(B) Terminal-modified polyethylene terephthalate]
The (B) terminal-modified polyethylene terephthalate according to the present invention is a polyethylene whose terminal is modified with a group represented by the following general formula (1), or a group represented by the following general formula (1) and a carboxylic acid metal salt. It is terephthalate. In the following formula (1), the alkylene group having 1 to 12 carbon atoms represented by X includes a methylene group, an ethylene group, a 1,3-propylene group, a 1,4-butylene group, a 1,5-pentylene group, 1 1,6-hexylene group, 1,2-butylene group, 1,2-pentylene group, 1,2-hexylene group, 1,9-nonylene group, 1,10-decylene group, 1,11-undecylene group, , 12-dodecylene group and the like, and an ethylene group is preferable.

(In the formula, X represents a direct bond or an alkylene group having 1 to 12 carbon atoms.)

  (B) The average molecular weight of the end-modified polyethylene terephthalate is not particularly limited, and any molecular weight can be selected. However, if it is smaller than 200, the retention in the polyester resin is poor, and bloom appears on the surface of the molded product. When it exceeds 20000, the effect as a crystal nucleating agent may not be exhibited, so 200 to 20000 is preferable, and 500 to 10,000 is more preferable.

  In the polyester resin composition of the present invention, with respect to a total of 100 parts by mass of (A) the polyester resin and (B) the remainder obtained by removing the group represented by the above general formula (1) from the terminal-modified polyethylene terephthalate, the above general formula It is preferable that content of group represented by (1) is 0.001-5 mass parts, and it is more preferable that it is 0.005-0.5 mass parts.

（式（２）中、ｎは、１又は２を表し、Ｍは水素原子又は金属原子を表し、ｎが１の場合、Ｍは水素原子又はアルカリ金属を表し、ｎが２の場合、Ｍは２価の金属原子を表す。）

（式（３）中、Ａは炭素原子数１〜１２のアルキレン基を表す。） As a method of modifying the terminal of polyethylene terephthalate with the group represented by the general formula (1), that is, a method of introducing the group, a polymer in which the terminal of polyethylene terephthalate is modified with a halogen or a halogenated alkylene group and the following general formula: A method of reacting the compound represented by (2), a method of polymerizing a compound represented by the following general formula (3) as a polymerization monomer (stopper) during polymerization of polyethylene terephthalate, the following general formula (2) Or the method etc. which dissolve the compound represented by (3) in the diol component of a monomer, and are added at the time of the polymerization of a polyethylene terephthalate are mentioned.

(In formula (2), n represents 1 or 2, M represents a hydrogen atom or a metal atom, when n is 1, M represents a hydrogen atom or an alkali metal, and when n is 2, M represents Represents a divalent metal atom.)

(In formula (3), A represents an alkylene group having 1 to 12 carbon atoms.)

  Examples of the alkylene group having 1 to 12 carbon atoms represented by A in the general formula (2) include the same alkylene groups as described above, and an ethylene group is preferable. The metal atom represented by M in the general formula (2) is selected from lithium, potassium, sodium, magnesium, calcium, strontium, barium, titanium, manganese, iron, zinc, silicon, zirconium, yttrium or barium. Metal. Potassium, lithium, and sodium are preferable because a crystal nucleating agent excellent in the crystallization accelerating effect of the polyester resin is obtained, and sodium is particularly preferable.

  In addition, when the compound represented by the general formula (2) or the general formula (3) is directly introduced into polyethylene terephthalate, the polymerization is performed by introducing these compounds into the reaction system following the polymerization of polyethylene terephthalate. If it continues, what was chemically couple | bonded with the terminal of polyethylene terephthalate will be obtained.

  As another terminal modification method for polyethylene terephthalate, a compound represented by the above general formula (2), or a compound represented by the above general formula (3) and a carboxylic acid metal salt are added after polymerization of polyethylene terephthalate. And mixing and heating and melting.

  When the compound represented by the general formula (2) or the general formula (3) is used, it is preferable to use a compound that has been pulverized. The pulverization is performed using a pulverizer until the volume average particle diameter is preferably in the range of 0.5 to 50 μm, more preferably 1 to 30 μm. Further, it is preferable that the 250 μm mesh pass is 90% by mass or more, more preferably 95% by mass or more by pulverization.

  When the volume average particle diameter is less than 0.5 μm, energy consumption required for pulverization is large and uneconomical. When it exceeds 50 μm, an end-modified polyethylene terephthalate prepared using the above pulverized product is blended with a polyester resin for molding. In this case, the compound represented by the general formula (2) or (3) may be aggregated without being dispersed in the polyethylene terephthalate, and the final appearance of the molded product may be impaired. If the 250 mesh pass is less than 90% by mass, coarse particles may remain unmelted in the resin during melt kneading with polyethylene terephthalate, which may adversely affect the appearance and physical properties of the molded product.

  In the present invention, the volume average particle diameter represents a numerical value at which the volume average by a laser diffraction / accumulation type particle size distribution meter (trade name: Microtrac MT3000II, manufactured by Nikkiso Co., Ltd.) is 50%.

  As the pulverizer used for the pulverization, a known pulverizer can be used. For example, a roll-type pulverizer, a high-speed rotational impact pulverizer, an airflow-type pulverizer, a shearing / grinding-type pulverization method, and a pulverizer using a medium-type pulverizer are preferably used. A combination of these pulverization methods may be used, or a combination of pulverization equipment may be used. A system that introduces a classification mechanism can also be adopted.

  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 high-speed rotational impact pulverizer include those that collide a sample with a rotor that rotates at high speed and achieve miniaturization by the impact force. Specifically, a hammer mill type hammer type with a fixed or swinging impactor attached to the rotor, a pin mill type rotary disk type with a pin or impact head attached to a rotating disc, and the sample is conveyed in the shaft direction. Examples thereof include an axial flow type for pulverization and an annular type for finer particles in a narrow annular portion.

  The airflow crusher (jet mill) is a device that uses the kinetic energy of a high-speed gas fluid to accelerate and collide the sample and crush the particles by directly colliding with the collision plate. And a type that is mainly responsible for pulverization by making fine particles by friction between particles.

  Examples of the shearing / grinding type pulverizer include a grinding type pulverizer using shear friction force under pressure.

  As the above-mentioned medium type pulverizer, a container driven mill that drives an internal pulverizing medium by moving the container rotating or vibrating, and a medium agitating type that imparts a kinetic force to the medium by an agitation mechanism inside the container. Mill. 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, and a high swing mill. The medium agitating mill includes a tower shape, an agitation, depending on the shape of the container. Examples include a tank type, a distribution pipe type, and an annular type.

  The grinding media are solid, for example, non-metal such as glass, meno, silicon nitride, zirconia, steatite, etc., metal such as alumina, titania, tungsten carbide, chrome steel, stainless steel The thing made from alloys, such as these, is mentioned. Although it does not limit as a form, For example, a bead and a ball-like thing are mentioned.

  When the pulverization treatment is performed, it is preferable that the compound represented by the general formula (2) or the general formula (3) is dried until the moisture content is 8 mass% or less, and then the pulverization treatment is performed, and the mass is preferably 5 mass% or less. It is more preferable to carry out after drying until. If the water content exceeds 8% by mass, the pulverization time may be prolonged and the pulverization efficiency may deteriorate, the pulverized products may adhere to each other in the pulverization tank and harden, or secondary aggregation may occur after pulverization. Moreover, drying until the moisture content is less than 0.01% by mass is uneconomical.

  In addition, the said moisture content is the weight reduction amount of the sample 10g on the measurement conditions of standard mode measurement accuracy HI and sample dish temperature 160 degreeC using the heat drying type moisture meter MS-70 by A & D Co., Ltd. The amount of water contained in the measurement sample was evaluated, and the ratio between the amount of water and the weight of the measurement sample was evaluated as the moisture content.

  In addition, when the compound represented by the general formula (2) or (3) is heated and melted with polyethylene terephthalate, the compound represented by the general formula (2) or (3) is pulverized and further 1% by mass. It is preferable to use one that has been dried to the following moisture content. When a terminal-modified polyethylene terephthalate produced using 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 uneconomical to dry until it is less than 0.01% by mass. As a drying method, a known dryer can be used. For example, a spray dryer, a vacuum freeze dryer, a vacuum dryer, a mobile dryer, a fluidized bed dryer, a rotary observer, a stirring dryer, and the like may be used.

  When the pulverized products are aggregated by weak interparticle attractive force, it is preferable to disintegrate the aggregate. As a device for crushing, a known crushing treatment device can be used, and examples thereof include a jet mill and a Henschel mill.

  Examples of the carboxylic acid metal salt include lithium carboxylic acid salt, potassium carboxylic acid salt, sodium carboxylic acid salt and the like, and sodium carboxylic acid salt is particularly preferable.

[Other additives]
The polyester resin composition of the present invention may further contain other additives as necessary. Examples of other additive compounding methods include a method of mixing with a polyester resin in a compounding amount according to the purpose, and melt-kneading with a molding processing machine such as an extruder, and granulating and molding. Other additives may be mixed and added together with the crystal nucleating agent. After melt-kneading the polyester resin composition of the present invention, other additives are added and molded using a molding machine. May be.

  Examples of other additives include plasticizers, fillers, phenolic antioxidants, phosphorus antioxidants, thioester antioxidants, ultraviolet absorbers, hindered amine compounds, heavy metal deactivators, and crystals used in the present invention. Examples include crystal nucleating agents other than nucleating agents, flame retardants, metal soaps, hydrotalcite, fillers, lubricants, antistatic agents, pigments, and dyes.

  When 0.1 to 20 parts by mass of at least one of a plasticizer, particularly a polyether ester plasticizer and / or a benzoate plasticizer is contained, the moldability of the polyester resin and the shrinkage anisotropy of the resulting molded product It is preferable because it is possible to improve the properties and surface characteristics.

  Examples of the plasticizer include polyethylene glycol butanoic acid ester, polyethylene glycol isobutanoic acid ester, polyethylene glycol di (2-ethylbutyric acid) ester, polyethylene glycol (2-ethylhexylic acid) ester, polyethylene glycol decanoic acid ester, and adipic acid diacid. Butoxyethanol, di (butyl diglycol) adipate, di (butyl polyglycol) adipate, di (2-ethylhexyloxyethanol) adipate, di (2-ethylhexyl diglycol) adipate, di (2- Ethylhexyl polyglycol), dioctoxyethanol adipate, di (octyl diglycol) adipate, di (octyl polyglycol) adipate, ethylene glycol benzoate, Ethylene glycol dibenzoate, polyethylene glycol dibenzoate, propylene glycol dibenzoate, dipropylene glycol dibenzoate, tripropylene glycol dibenzoate, 1,3-butanediol dibenzoate, 1, 4-butanediol benzoate, 1,6-hexanediol dibenzoate, 3-methyl-1,5-pentanediol dibenzoate, 1,8-octenediol dibenzoate, Sanyo Chemical Industries, Ltd. ) Product name EP-400 and a polyester plasticizer having a polybasic acid and a polyhydric alcohol condensate as a basic structure, both ends of which are terminated with a monohydric alcohol or a monobasic acid.

  As said polybasic acid, what is known as a monomer for polyesters can be used. For example, aromatic carboxylic acids such as terephthalic acid, isophthalic acid, trimellitic acid, pyromellitic acid and naphthalenedicarboxylic acid, aliphatic carboxylic acids such as maleic acid, fumaric acid, succinic acid, alkenyl succinic acid and adipic acid, Examples thereof include methyl ester compounds of basic acids and anhydrides thereof. A polybasic acid can be used alone or in combination of two or more.

  As said polyhydric alcohol, what is known as a monomer for polyesters can be used, for example, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 2-methyl-1,3-propanediol, 1, 4-butanediol, 1,5-pentanediol, 2,2-dimethyl1,3-propanediol (neopentyl glycol), 2,2-diethyl-1,3-propanediol (3,3-dimethylolpentane) 2-n-butyl-2-ethyl-1,3-propanediol, (3,3-dimethylolheptane), 3-methyl-1,5-pentanediol-1,6-hexanediol, 2,2, 4-trimethyl-1,3-pentanediol, 2-ethyl 1,3-hexanediol, 2-methyl-1,8-octane C2-C18 aliphatic polyhydric alcohols such as all, 1,9-nonanediol, 1,10-decanediol, 1,12-octadecanediol, glycerin, cyclohexanediol, cyclohexanedimethanol, hydrogenated bisphenol A And aromatic diols such as bisphenol A ethylene oxide adduct and bisphenol A propylene oxide adduct. A polyhydric alcohol may be used individually by 1 type, or may use 2 or more types together.

  Specific examples of the monohydric alcohol include, for example, octanol, isooctanol, 2-ethylhexanol, nonanol, isononanol, 2-methyloctanol, decanol, isodecanol, undecanol, dodecanol, tridecanol, tetradecanol, hexadecanol, 8-18 aliphatic alcohols such as octadecanol, alicyclic alcohols such as cyclohexanol, benzyl alcohol, 2-phenylethanol, 1-phenylethanol, 2-phenoxyethanol, 3-phenyl-1-propanol, 2- Aromatic alcohols such as hydroxyethyl benzyl ether are listed. A monohydric alcohol may be used individually by 1 type, and may use 2 or more types together.

  Specific examples of the monobasic acid include monocarboxylic acids such as caprylic acid, nonanoic acid, capric acid, undecyl acid, lauric acid, monoesters of dicarboxylic acid, and diesters of tricarboxylic acid. A basic acid may be used individually by 1 type, and may use 2 or more types together.

  Examples of the plasticizer other than the above-described plasticizer include alicyclic ester plasticizers. Examples thereof include cyclohexanedicarboxylic acid esters, cyclohexanedicarboxylic acid esters having an epoxy group, and cyclohexanedicarboxylic acid anhydrides such as 1,2-cyclohexanedicarboxylic acid anhydride.

  Still other plasticizers include, for example, ethyl benzyl phthalate, butyl benzyl phthalate, isobutyl benzyl phthalate, heptyl benzyl phthalate, (2-ethylhexyl) benzyl phthalate, n-octyl benzyl phthalate, nonyl benzyl phthalate, isononyl benzyl phthalate, iso Decyl benzyl phthalate, undecyl benzyl phthalate, tridecyl benzyl phthalate, cyclohexyl benzyl phthalate, benzyl-3- (isobutyryloxy) -1-isopropyl-2,2-dimethylpropyl phthalate, myristyl benzyl phthalate, dibutyl phthalate, diisobutyl phthalate , Diheptyl phthalate, di- (2-ethylhexyl) phthalate, di-n-octyl phthalate, dinonyl phthalate Phthalate ester plasticizers such as diisononyl phthalate, diisodecyl phthalate, diundecyl phthalate, ditridecyl phthalate, dicyclohexyl phthalate and diphenyl phthalate, and isophthalic acid esters such as di- (2-ethylhexyl) isophthalate and diisooctyl isophthalate , Tetrahydrophthalic acid esters such as di-2-ethylhexyl tetrahydrophthalate, adipic acid esters such as di- (2-ethylhexyl) adipate, dibutoxyethyl adipate, diisononyl adipate, di-n-hexyl azelate, di- Azelaic acid esters such as (2-ethylhexyl) azelate, sebacic acid esters such as di-n-butyl sebacate, di-n-butyl maleate, di- (2-ethylhexyl) Maleate esters such as reate, fumarate esters such as di-n-butyl fumarate, di- (2-ethylhexyl) fumarate, tri- (2-ethylhexyl) trimellitate, tri-n-octyl trimellitate, tri Trimellitic acid esters such as isooctyl trimellitate, pyromellitic acid esters such as tetra- (2-ethylhexyl) pyromellitate, tetra-n-octyl pyromellitate, tri-n-butyl citrate, acetyltributyl citrate Citrates such as dimethyl itaconate, diethyl itaconate, dibutyl itaconate, itaconic acid esters such as di- (2-ethylhexyl) itaconate, ricinoleic acid derivatives such as glycerin monoricinolate and diethylene glycol monoricinoleate, Stearate esters such as glycerin monostearate, diethylene glycol distearate, other fatty acid esters such as diethylene glycol dipelargonate, pentaerythritol fatty acid ester, tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate, diphenyl decyl phosphate, Examples thereof include phosphate esters such as diphenyloctyl phosphate. Said other plasticizer may be used individually by 1 type, and may use 2 or more types together.

  A preferable blending amount of the plasticizer is 0.000 based on a total of 100 parts by mass of (A) the polyester resin and (B) the remainder obtained by removing the group represented by the general formula (1) from the terminal-modified polyethylene terephthalate. 1 to 20 parts by mass, more preferably 0.5 to 15 parts by mass, even more preferably 1 to 10 parts by mass, and most preferably 1 to 5 parts by mass. If the amount is less than 0.1 parts by mass, the effect may not be sufficient. If the amount exceeds 20 parts by mass, the plasticizer may bleed out.

  In the present invention, an inorganic filler can be further used. The use of inorganic fillers gives the molded product rigidity such as mechanical strength, makes it a molded product with little anisotropy and warpage, and adjusts the fluidity during the melt processing of the polyester resin composition. be able to. The inorganic filler may be appropriately selected from those used for reinforcing conventional thermoplastic resins according to the purpose.

  Examples of the inorganic filler include talc, mica, calcium carbonate, calcium oxide, calcium hydroxide, magnesium carbonate, magnesium hydroxide, magnesium oxide, magnesium sulfate, aluminum hydroxide, barium sulfate, glass powder, glass fiber, and clay. , Dolomite, mica, silica, alumina, potassium titanate whisker, wollastonite, fibrous magnesium oxysulfate, and the like, and the average particle diameter (spherical or flat) or the average fiber diameter (acicular or fibrous) The thing of 5 micrometers or less is preferable.

  In order to impart rigidity such as mechanical strength to the molded product, a fibrous shaped inorganic filler is preferably used, and glass fiber is particularly preferable. Further, in order to obtain a molded product having little anisotropy and warpage, an inorganic filler in the form of a plate-like material is preferable, and mica, glass flakes, and the like are particularly preferably used. Moreover, a granular inorganic filler is preferably used for adjustment of fluidity at the time of manufacturing a molded article.

  The blending amount of the inorganic filler is 0. 0 parts by mass with respect to 100 parts by mass in total of (A) the polyester resin and (B) the remainder obtained by removing the group represented by the general formula (1) from the terminal-modified polyethylene terephthalate. 01 to 400 parts by mass, preferably 1 to 300 parts by mass, more preferably 5 to 200 parts by mass, and still more preferably from the viewpoint of mechanical strength, rigidity, shrinkage anisotropy, and surface characteristics of the obtained molded product. Is 10 to 50 parts by mass. When the amount is less than 0.01 parts by mass, the mechanical strength and rigidity of the molded product may not be improved. When the amount exceeds 400 parts by mass, the appearance of the molded product may be impaired due to surface roughness.

  The said inorganic filler can also use what was previously processed with the surface treating agent in order to improve affinity and adhesiveness in an interface with a polyester resin. As the surface treatment agent, for example, a surface treatment agent containing one or more of an aminosilane compound and an epoxy resin is preferably used.

  Examples of the aminosilane compound include γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, and γ- (2-aminoethyl) aminopropyltrimethoxysilane.

  The epoxy resin contained in the surface treatment agent is roughly classified into, for example, a novolac type epoxy resin and a bisphenol type epoxy resin, and a novolac type epoxy resin is preferably used. Examples of the novolak type epoxy resin include polyfunctional type epoxy resins such as a phenol novolak type epoxy resin and a cresol novolak type epoxy resin.

  In addition to the aminosilane compound and the epoxy resin, the surface treatment agent may contain components such as a urethane resin, an acrylic resin, an antistatic agent, a lubricant, and a water repellent as long as the properties are not impaired. . Furthermore, as other surface treatment agents, epoxy resins other than novolac type and bisphenol type, coupling agents and the like can be mentioned.

Examples of the phenolic antioxidant include 2,6-di-t-butyl-4-ethylphenol, 2-t-butyl-4,6-dimethylphenol, styrenated phenol, 2,2′-methylenebis ( 4-ethyl-6-tert-butylphenol), 2,2′-thiobis- (6-tert-butyl-4-methylphenol), 2,2′-thiodiethylenebis [3- (3,5-di-t -Butyl-4-hydroxyphenyl) propionate], 2-methyl-4,6-bis (octylsulfanylmethyl) phenol, 2,2'-isobutylidenebis (4,6-dimethylphenol), isooctyl-3- ( 3,5-di-tert-butyl-4-hydroxyphenyl) propionate, N, N′-hexane-1,6-diylbis [3- (3,5-di-tert-butyl-4-hydride) Xylphenyl) propionamide, 2,2′-oxamido-bis [ethyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2-ethylhexyl-3- (3 ′, 5′- Di-t-butyl-4′-hydroxyphenyl) propionate, 2,2′-ethylenebis (4,6-di-t-butylphenol), 3,5-bis (1,1-dimethylethyl) -4-hydroxy -Ester of benzenepropanoic acid and C13-15 alkyl, 2,5-di-t-amylhydroquinone, polymer of hindered phenol (trade name AO.OH998 manufactured by Adeka Palmaloma), 2,2'-methylenebis [6 -(1-methylcyclohexyl) -p-cresol], 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl)- 4-methylphenyl acrylate, 2- [1- (2-hydroxy-3,5-di-t-pentylphenyl) ethyl] -4,6-di-t-pentylphenyl acrylate, 6- [3- (3- t-butyl-4-hydroxy-5-methyl) propoxy] -2,4,8,10-tetra-t-butylbenz [d, f] [1,3,2] -dioxifobin, hexamethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, bis [monoethyl (3,5-di-tert-butyl-4-hydroxybenzyl) phosphonate calcium salt, 5,7-bis ( 1,1-dimethylethyl) -3-hydroxy-2 (3H) -benzofuranone and the reaction product of o-xylene, 2,6-di-t-butyl-4- (4,6-bis (octylthio) -1 3,5-triazin-2-ylamino) phenol, DL-a-tocophenol (vitamin E), 2,6-bis (α-methylbenzyl) -4-methylphenol, bis [3,3-bis- (4 '-Hydroxy-3'-t-butyl-phenyl) butanoic acid] glycol ester, 2,6-di-t-butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, stearyl (3,3 5-di-t-butyl-4-hydroxyphenyl) propionate, distearyl (3,5-di-t-butyl-4-hydroxybenzyl) phosphonate, tridecyl-3,5-di-t-butyl-4-hydroxy Benzylthioacetate, thiodiethylenebis [(3,5-di-t-butyl-4-hydroxyphenyl) propionate], 4,4′-thiobis ( 6-t-butyl-m-cresol), 2-octylthio-4,6-di (3,5-di-t-butyl-4-hydroxyphenoxy) -s-triazine, 2,2′-methylenebis (4- Methyl-6-tert-butylphenol), bis [3,3-bis (4-hydroxy-3-tert-butylphenyl) butyric acid] glycol ester, 4,4′-butylidenebis (2,6-di-t-) Butylphenol), 4,4′-butylidenebis (6-tert-butyl-3-methylphenol), 2,2′-ethylidenebis (4,6-di-tert-butylphenol), 1,1,3-tris (2 -Methyl-4-hydroxy-5-t-butylphenyl) butane, bis [2-t-butyl-4-methyl-6- (2-hydroxy-3-t-butyl-5-methylbenzyl) phenyl] tere Phthalate, 1,3,5-tris (2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl) isocyanurate, 1,3,5-tris (3,5-di-tert-butyl-4- Hydroxybenzyl) isocyanurate, 1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, 1,3,5-tris [(3 5-di-t-butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate, tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] methane, 2 -T-butyl-4-methyl-6- (2-acryloyloxy-3-t-butyl-5-methylbenzyl) phenol, 3,9-bis [2- (3-t-butyl-4-hydroxy 5-methylhydrocinnamoyloxy) -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, triethylene glycol bis [β- (3-t-butyl-4 -Hydroxy-5-methylphenyl) propionate].
The amount of the phenolic antioxidant used is a total of 100 parts by mass of the (A) polyester resin and (B) the remainder obtained by removing the group represented by the general formula (1) from the terminal-modified polyethylene terephthalate. It is 0.001-10 mass parts, More preferably, it is 0.01-5 mass parts.

（一般式（４）中、Ｒ^１、Ｒ^２、Ｒ^３及びＲ^４は、各々独立して、水素原子、分岐を有してもよい炭素原子数１〜８のアルキル基、置換されていてもよい炭素原子数６〜１２のアリール基又は炭素原子数７〜１２のアラルキル基を表す）で表されるリン系酸化防止剤は、成形加工時の着色防止効果が特に優れるので好ましい。 Examples of the phosphorus antioxidant include triphenyl phosphite, diisooctyl phosphite, heptakis triphosphite, triisodecyl phosphite, diphenylisooctyl phosphite, diisooctyloctylphenyl phosphite, diphenyltridecyl Phosphite, triisooctyl phosphite, trilauryl phosphite, diphenyl phosphite, tris (dipropylene glycol) phosphite, diisodecyl pentaerythritol diphosphite, dioleyl hydrogen phosphite, trilauryl trithiophosphite, bis (tridecyl) ) Phosphite, tris (isodecyl) phosphite, tris (tridecyl) phosphite, diphenyldecyl phosphite, dinonylphenyl bis (nonyl fe) Phosphite, poly (dipropylene glycol) phenyl phosphite, tetraphenyldipropyl glycol diphosphite, trisnonylphenyl phosphite, tris (2,4-di-t-butylphenyl) phosphite, tris (2, 4-di-tert-butyl-5-methylphenyl) phosphite, tris [2-tert-butyl-4- (3-tert-butyl-4-hydroxy-5-methylphenylthio) -5-methylphenyl] phos Phyto, tridecyl phosphite, octyl diphenyl phosphite, di (decyl) monophenyl phosphite, distearyl pentaerythritol diphosphite, a mixture of distearyl pentaerythritol and calcium stearate, alkyl (C10) bisphenol A phosphite, Di (Tori Syl) pentaerythritol diphosphite, di (nonylphenyl) pentaerythritol diphosphite, bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-t-butyl-) 4-methylphenyl) pentaerythritol diphosphite, bis (2,4,6-tri-t-butylphenyl) pentaerythritol diphosphite, bis (2,4-dicumylphenyl) pentaerythritol diphosphite, tetraphenyl Tetra (tridecyl) pentaerythritol tetraphosphite, bis (2,4-di-t-butyl-6-methylphenyl) ethyl phosphite, tetra (tridecyl) isopropylidenediphenol diphosphite, tetra (tridecyl) -4 , 4'-n-Butylidenebis 2-t-butyl-5-methylphenol) diphosphite, hexa (tridecyl) -1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butanetriphosphite, tetrakis (2,4 -Di-t-butylphenyl) biphenylene diphosphonite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, (1-methyl-1-propanyl-3-ylidene) tris ( 2-1,1-dimethylethyl) -5-methyl-4,1-phenylene) hexatridecyl phosphite, 2,2′-methylenebis (4,6-tert-butylphenyl) -2-ethylhexyl phosphite, 2 , 2′-methylenebis (4,6-di-t-butylphenyl) -octadecyl phosphite, 2,2′-ethylidenebis (4 6-di-t-butylphenyl) fluorophosphite, 4,4'-butylidenebis (3-methyl-6-t-butylphenylditridecyl) phosphite, tris (2-[(2,4,8,10- Tetrakis-t-butyldibenzo [d, f] [1,3,2] dioxaphosphin-6-yl) oxy] ethyl) amine, 3,9-bis (4-nonylphenoxy) -2,4 8,10-tetraoxa-3,9-diphosphasspiro [5,5] undecane, 2,4,6-tri-tert-butylphenyl-2-butyl-2ethyl-1,3-propanediol phosphite, Poly 4,4′-isopropylidenediphenol C12-15 alcohol phosphite, phosphat of 2-ethyl-2-butylpropylene glycol and 2,4,6-tri-tert-butylphenol Although DOO etc., the following general formula (4),

(In General Formula (4), R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms which may have a branch, or a substituted group. A phosphorous antioxidant represented by an aryl group having 6 to 12 carbon atoms or an aralkyl group having 7 to 12 carbon atoms is preferable because it has a particularly excellent anti-coloring effect during molding.

  The phosphorous antioxidant is used in an amount of 100 parts by mass in total of the (A) polyester resin and (B) the remainder obtained by removing the group represented by formula (1) from the terminal-modified polyethylene terephthalate. It is 0.001-10 mass parts, More preferably, it is 0.01-5 mass parts. If it is 0.001 part by mass or less, the polyester resin composition may not be able to obtain a sufficient stabilizing effect. If it exceeds 10 parts by mass, dispersion in the resin may be reduced, or the appearance of the molded product may be adversely affected. May give.

Examples of the alkyl group having 1 to 8 carbon atoms represented by R ¹ , R ² , R ³ and R ⁴ in the general formula (4) include methyl group, ethyl group, propyl group, isopropyl group, butyl, Examples include dibutyl, tert-butyl, isobutyl, amyl, isoamyl, tert-amyl, hexyl, cyclohexyl, heptyl, isoheptyl, tert-heptyl, n-octyl, isooctyl, tert-octyl, 2-ethylhexyl trifluoromethyl and the like. Moreover, the hydrogen atom in these groups may be substituted with a halogen atom, a saturated alicyclic ring, an aromatic ring or the like. Examples of the aryl group having 6 to 12 carbon atoms that may be substituted include a phenyl group and a naphthyl group. Examples of the aralkyl group having 6 to 12 carbon atoms include a hydrogen atom of the above alkyl group as an aryl group. And those substituted with a group.

Examples of the thioester antioxidant include tetrakis [methylene-3- (laurylthio) propionate] methane, bis (methyl-4- [3-n-alkyl (C12 / C14) thiopropionyloxy] 5-t-butyl. Phenyl) sulfide, ditridecyl-3,3′-thiodipropionate, dilauryl-3,3′-thiodipropionate, dimyristyl-3,3′-thiodipropionate, distearyl-3,3′-thiodipro Pionate, lauryl / stearyl thiodipropionate, 4,4'-thiobis (6-t-butyl-m-cresol), 2,2'-thiobis (6-t-butyl-p-cresol), distearyl- Disulfide is mentioned.
The amount of the thioester-based antioxidant used is preferably 100 parts by mass in total of (A) the polyester resin and (B) the remainder obtained by removing the group represented by the general formula (1) from the terminal-modified polyethylene terephthalate. And 0.01 to 0.3 parts by mass.

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 ultraviolet absorber is used in an amount of 0.1 parts per 100 parts by mass in total of (A) the polyester resin and (B) the remainder obtained by removing the group represented by the general formula (1) from the terminal-modified polyethylene terephthalate. It is 001-5 mass parts, 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, trade name: TINUVIN NOR 371 manufactured by Ciba.
The amount of the hindered amine light stabilizer used is a total of 100 parts by mass of the (A) polyester resin and (B) the remainder obtained by removing the group represented by the general formula (1) from the terminal-modified polyethylene terephthalate. It is 0.001-5 mass parts, 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 tantalate, calcium montanate, sodium benzoate, potassium benzoate, calcium benzoate, 4-tert-butylaluminum benzoate, sodium adipate and disodium bicyclo [2.2.1] heptane-2,3- Carboxylic acid metal salts such as dicarboxylate, sodium carbonate, magnesium carbonate; sodium bis (4-tert-butylphenyl) phosphate, sodium-2,2′-methylenebis (4,6-ditert-butylphenyl) phosphate and lithium Phosphate metal salts such as -2,2'-methylenebis (4,6-ditertiarybutylphenyl) phosphate; dibenzylidene sorbitol, bis (methylbenzylidene) sorbitol, bis (p-ethylbenzylidene) sorbitol, and bis ( Dimethyl benzylidene ) Polyhydric alcohol derivatives such as sorbitol; N, N ′, N ″ -tris [2-methylcyclohexyl] -1,2,3-propanetricarboxamide, N, N ′, N ″ -tricyclohexyl-1,3 Amide compounds such as 5-benzenetricarboximide, N, N′-dicyclohexyl-naphthalenedicarboxamide, 1,3,5-tris (2,2-dimethylpropionylamino) benzene; polycaprolactone, polyglycol, polyolefin, nylon 6 , Polymer materials such as polytetrafluoroethylene powder, high melting point polyester resin, polyester oligomer and alkali metal salts thereof.
The amount of the other crystal nucleating agent used is based on a total of 100 parts by mass of the remainder obtained by removing the group represented by the general formula (1) from the (A) polyester resin and (B) terminal-modified polyethylene terephthalate. The total amount with the crystal nucleating agent used by this invention is used so that it may become 0.001-1 mass part.

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 with respect to a total of 100 mass parts of the remainder remove | excluding the group represented by General formula (1) from the said (A) polyester resin and (B) terminal modification polyethylene terephthalate. It is 10-30 mass parts, More preferably, it is 10-30 mass parts.

The above-mentioned lubricant is added for the purpose of imparting lubricity to the surface of the molded body and enhancing the effect of preventing damage. Examples of the lubricant include unsaturated fatty acid amides such as oleic acid amide and erucic acid amide; saturated fatty acid amides such as behenic acid amide and stearic acid amide. These may be used alone or in combination of two or more.
The addition amount of the lubricant is 0.03 to 2 with respect to 100 parts by mass in total of (A) the polyester resin and (B) the remainder obtained by removing the group represented by the general formula (1) from the terminal-modified polyethylene terephthalate. It is the range of 0.04-1 mass part more preferably mass part. If the amount is less than 0.03 parts by mass, the desired lubricity may not be obtained. If the amount exceeds 2 parts by mass, the lubricant component may bleed on the surface of the molded product or cause a decrease in physical properties.

  The antistatic agent is added for the purpose of reducing the chargeability of the molded body and preventing dust from adhering due to charging. Examples of the antistatic agent include a cationic antistatic agent, an anionic antistatic agent, and a nonionic antistatic agent. Preferred examples include polyoxyethylene alkylamines, polyoxyethylene alkylamides or their fatty acid esters, glycerin fatty acid esters, and the like. These may be used alone or in combination of two or more. Moreover, the addition amount of the antistatic agent is preferably 100 parts by mass in total of the (A) polyester resin and (B) the remainder obtained by removing the group represented by the general formula (1) from the terminal-modified polyethylene terephthalate. It is 0.03-2 mass parts, More preferably, it is 0.04-1 mass parts. When the amount of the antistatic agent is too small, the antistatic effect is insufficient. On the other hand, when the amount is too large, bleeding to the surface and deterioration of physical properties may occur.

Moreover, a release agent can be mix | blended with the polyester resin composition of this invention. The mold release agent is preferably one that improves the mold release property of the molded product from the mold and enables the molded product to be released even with a mold having a cavity with a reverse taper surface. Specific examples include polyethylene wax and low molecular weight polypropylene, which can be used alone or in combination. Here, the polyethylene wax is a low molecular weight polyethylene having a molecular weight of about 500 to 10,000.
The addition amount of the mold release agent is 0.1 to 100 parts by mass in total of the (A) polyester resin and (B) the remainder obtained by removing the group represented by the general formula (1) from the terminal-modified polyethylene terephthalate. 1 part by mass is preferred.

  The polyester resin composition of the present invention can be molded using a known molding method or molding apparatus. For example, it can be molded by any molding method such as extrusion molding, injection molding, hollow molding, blow molding, calendar molding, compression molding, sheet, film, housing, food container, cosmetic container, bottle, tank, etc. Containers, food bottles, beverage bottles, edible oil bottles, seasoning bottles and other bottles, food packaging materials, wrapping materials, packaging materials for transport packaging materials, protective films for electronic materials, protective sheets for electrical appliances It can be used for sheets and films such as daily goods, toys, textile materials and the like.

  The molded body of the present invention may be stretched, and as a stretching method, after preforming, it is stretched by applying stress so as to be stretched in a stretching direction uniaxially or biaxially, or a cylindrical shape (bottle container) ) Is stretched. Stretching is usually performed in a temperature range of 80 to 200 ° C.

  When the polyester resin composition of the present invention is used for a fiber material, the polyester resin composition may be melted and stretched, and a stretched and oriented fiber is particularly preferable. As the stretching method, a known stretching method can be used, and the stretching ratio can be determined within a range where the fiber is not broken.

  The fiber can be subjected to twisting, adhesive treatment, heat treatment, and alkali treatment by a known method, and the twisted yarn may be twisted with a fiber material other than the polyester fiber. As the other fiber material, a material that is easily entangled with the polyester fiber and has few fiber breakage is preferably used.

  The above fibers are vehicle tire structures, printing substrates, wallpaper substrates, wiping materials, various filter materials, poultice materials, medical hygiene materials such as sanitary products, clothing, clothing interlining, pillow covers, and cosmetics. It can be used for industrial materials such as base materials, automotive interior materials, sound absorbing materials, packaging materials, and civil engineering.

  When the polyester resin composition of the present invention is molded by an extrusion molding method, it is preferable that the screw temperature is within the melting point of polyethylene terephthalate plus 50 ° C. or less while supplying an inert gas such as nitrogen gas into the extruder. If the screw temperature is too low, a short circuit will occur and the molding will become unstable, and it will easily fall into an overload, and if the screw part temperature is too high, the resin will be thermally decomposed and the physical properties of the resulting molded product will be reduced. Since it may be colored, it is not preferable.

When the polyester resin composition of the present invention is molded into a plastic bottle, various blow molding methods can be used. The blow molding method is not particularly limited, and examples thereof include a direct blow method in which blow molding is performed after forming a preform by extrusion molding, and an injection blow molding method in which blow molding is performed after molding a preform (parison) by injection molding. It is done.
Examples of the latter injection blow molding method include a hot parison method (one-stage method) in which blow molding is continuously performed after preform molding, and 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.

  In addition to the case where the preform is composed of a single layer of polyester resin, the preform can be composed of two or more layers of polyester resin, and an inner layer and an outer layer composed of two or more layers of polyester resin. Further, an intermediate layer can be inserted, and the intermediate layer can be a barrier layer or an oxygen absorbing layer.

  Examples of the barrier layer include those that suppress the permeation of oxygen from the outside to the plastic bottle and prevent the contents from being altered, and are particularly suitable for plastic bottles for beverages containing carbon dioxide gas.

  The oxygen absorbing layer absorbs oxygen and prevents permeation of oxygen in the plastic bottle, and an oxidizable organic substance or a transition metal catalyst, or a resin having a high gas barrier property that does not substantially oxidize is used.

  In the above preform, when producing a multilayer preform having an oxygen absorbing layer as an intermediate layer, a known co-injection molding machine or the like is used, the inner and outer layers are made of polyester resin, and one or two layers between the inner and outer layers. In the production method of the present invention in which a multilayer preform can be produced by inserting the above oxygen absorbing layer, the preform can be produced by a known injection molding machine or extrusion molding machine.

  When the preform is formed by stretch blow, the preform is preferably stretched by heating at a temperature equal to or higher than the glass transition point of polyethylene terephthalate. Specifically, the film can be stretched within a range of 85 ° C to 135 ° C, more preferably 90 to 130 ° C. If the temperature is lower than 85 ° C, the preform cannot be softened sufficiently and stretch blow molding cannot be performed. If the temperature exceeds 135 ° C or the heating time is too long, crystallization of the preform proceeds excessively and uniform stretching can be achieved. Or the transparency of the plastic bottle may be reduced.

  The stretching is performed by stretch blow molding a preform heated at a predetermined temperature. The mold temperature is 85 to 160 ° C, more preferably 90 to 145 ° C. If it is less than 85 ° C., the heat shrinkage of the molded product may be remarkably unstable, and if it exceeds 160 ° C., thermal decomposition of the resin may increase, and foreign matter may easily adhere to the mold.

  In order to improve the heat resistance of the plastic bottle, the plastic bottle may be heat-treated. In the heat treatment, the obtained plastic bottle is heated to 180 to 245 ° C, more preferably 200 to 235 ° C, and the mold temperature is set to 100 to 230 ° C, more preferably 110 to 200 ° C. Remold. If the mold temperature is less than 100 ° C, sufficient heat resistance cannot be obtained, and if it is 230 ° C or more, the shape of the molded product may not be maintained.

  Moreover, the draw ratio in blow molding is not particularly limited, but is preferably 3 to 14 times, preferably 4 to 12 times in terms of longitudinal draw ratio x transverse draw ratio. If it is 14 times or more, whitening of the plastic bottle may occur due to overstretching. If it is less than 3 times, it is necessary to reduce the thickness of the preform, but if the preform is too thin, it will be formed into a uniform thickness. Becomes difficult.

  In addition, by crystallizing the bottle neck portion of the plastic bottle, it is possible to prevent deformation of the mouth portion of the plastic bottle due to high temperature filling. Insufficient mouth crystallization causes problems such as deformation when capping a plastic bottle, leakage of the contents after cooling the plastic bottle filled with contents, and loosening of the cap. There is a case. 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. As temperature to heat-crystallize, 160-200 degreeC is preferable and the range of 160-180 degreeC is more preferable.

  Moreover, when shape | molding the polyester resin composition of this invention as a plastic bottle for heat-resistant use, it is necessary to set the density of a plastic bottle to an appropriate value. If the density is too high, the degree of crystallinity of the plastic bottle will be excessively high, which may hinder blow molding.If the density is too low, the plastic bottle will be heated and deformed. May leak. The density is appropriately selected depending on the polyester resin.

Specific use examples of plastic bottles include normal bottles, carbonated bottles, hot filling bottles, hot compatible bottles, heat and pressure resistant bottles, etc. Applications include dairy products, tea, soft drinks, carbonated bottles, etc. Examples include beverage containers such as beverages, barley, wine, shochu, and sake, soy sauce, edible oil, salad dressings, containers for seasonings such as spices, detergent containers such as shampoos and rinses, cosmetic containers, and the like. Plastic bottles can be used from small bottles with a capacity of several ml to large bottles with a capacity of more than 5L. The thickness of the plastic is not particularly limited as long as it can protect the contents, and is usually preferably in the range of 0.1 mm to 1 mm at the thinnest part.
In addition, the outer surface of the plastic bottle is coated with a film such as polyethylene / polypropylene or a laminate film with ceramic / silica bonded together, or the bottle inside is deposited with metal oxide, amorphous carbon, etc. Can be used.

  When an aseptic filling system is employed for the plastic bottle, it can be employed in a known manner. Specifically, a system comprising a combination of a container sterilization section and an aseptic filling section can be mentioned.

  In the container sterilization section, the inside of the plastic bottle is washed with warm water or a chlorinated chemical containing hydrogen peroxide, peracetic acid, hypochlorous acid, ozone, etc. The plastic bottle is sterilized by a method such as injecting a sterilizing solvent or immersing it in a medicine, then the mouth of the plastic bottle is turned down, the sterilizing solvent or medicine is discharged, and the residue is removed with air or the like. Is called.

  In the aseptic filling section, a sterilized container is filled with sterilized contents and capped. Examples of the method for sterilizing the contents include a method of filtering bacteria by ultrafiltration and a method of instant sterilization by high-temperature and short-time sterilization.

  The upper limit temperature for filling the contents is 40 ° C, more preferably 30 to 40 ° C. However, when a cooling step is added after filling, an upper limit temperature of 50 to 60 ° C. can be adopted.

  When the polyester resin composition of the present invention is molded into a sheet shape, the molding method is not particularly limited, and known molding methods such as extrusion molding, injection molding, hollow molding, blow, film, and sheet can be used. However, in the case of extrusion molding, the temperature condition of the extrusion molding machine is preferably such that the screw part temperature is within the melting point of the polyester resin plus 50 ° C. If the screw temperature is too low, a short circuit will occur and the molding will become unstable, and it will easily fall into an overload, and if the screw part temperature is too high, the resin will be thermally decomposed and the physical properties of the resulting molded product will be reduced. Since it may be colored, it is not preferable.

  In the present invention, the stretching of the molded body means that after the polyester resin is pre-molded, it is stretched by applying stress so as to be stretched in the stretching direction uniaxially or biaxially, or in a cylindrical shape (bottle container). Represents stretching, usually in the temperature range of 80-200 ° C

  The heating method is preferably one that can uniformly heat the entire molded body without any particular limitation, but may be one that heats a part or a plurality of parts.

  In the present invention, the molded product represents a product molded by a known molding method such as extrusion molding, injection molding, hollow molding, blow molding, compression molding, etc., and is a food container, a cosmetic / clothing container, a food bottle. Bottles for beverages, edible oil bottles, seasoning bottles, packaging materials for food packaging materials, wrapping materials, transportation packaging materials, protective films for electronic materials, sheets and films for protective sheets for electrical appliances, It can be used for daily goods and toys.

  Hereinafter, the present invention will be described more specifically with reference to production examples and examples. However, the present invention is not limited to the following examples.

[Production Example 1]
After mixing 0.3 parts by mass of the test compound shown in Table 1 below with 100 parts by mass of polyethylene terephthalate resin (TR-8550; manufactured by Teijin Chemicals Ltd.) dried under reduced pressure at 140 ° C. for 3 hours, a single-screw extruder (Laboplast mill mu; manufactured by Toyo Seiki Seisakusho Co., Ltd.) was used for melt kneading at a cylinder temperature of 270 ° C. and a screw speed of 150 rpm to obtain pellet A. The obtained pellet A was dried at 140 ° C. for 3 hours and used in the following Examples and Comparative Examples.

[Production Example 2]
In the said manufacture example 1, it manufactured like the manufacture example 1 except having changed the compounding quantity of the test compound from 0.3 mass part to 3 mass parts, and obtained the pellet B.

[Example 1, Comparative Examples 1 to 4]
The pellet A obtained in Production Example 1 or the pellet B obtained in Production Example 2 was blended with polyethylene terephthalate (TR-8550 manufactured by Teijin Chemicals Ltd.). The pellet was blended so that the pellet A or B was 6.67 parts by mass with respect to 100 parts by mass in total of the polyethylene terephthalate and the pellets A or B. Polyethylene terephthalate blended with pellets was mixed and granulated with a twin-screw extruder (equipment: TEX28V manufactured by Nippon Steel Works, cylinder temperature: 270 ° C., screw speed: 200 rpm) to obtain pellets. However, in Comparative Example 1 and Comparative Example 2 below, pellets were obtained by granulating with a twin screw extruder without adding pellet A and pellet B.

  About the obtained pellet, a 90 mm × 90 mm × 1 mm sheet was molded by an injection molding machine (Injection molding machine EC100 manufactured by Toshiba Corporation) (molding conditions: injection temperature 280 ° C., injection time 15 seconds, mold temperature 15 ° C., mold The mold cooling time was 20 seconds).

About the obtained sheet | seat, a biaxial stretching apparatus is set on the conditions of setting temperature: 97 degreeC and stretching speed: 2.5 mm / min in both length and width in a biaxial stretching apparatus (EX-10B manufactured by Toyo Seiki Seisakusho Co., Ltd.). After confirming that the temperature was stable, the sheet was placed, allowed to stand for 2.5 minutes, and then stretched 4 times in length and width. The obtained stretched sheet was measured by the following method. These results are shown in Table 1 below.
In addition, the annealing process implemented in the following Example 2 and Comparative Example 2 refers to the obtained stretched sheet, a flat heater heated to 180 ° C., a height of 10 mm from the top surface of the stretched sheet, and the bottom surface Installed at a height of 20 mm and allowed to stand for 1 minute.

(1) Yellowness (YI)
In accordance with JIS K7105, the yellowness (YI) of the test piece was measured with a spectrocolorimeter (SC-P; manufactured by Suga Test Instruments Co., Ltd.).

(2) Transparency Based on JIS K7361, -K7136, ISO-13468, -14787, Haze [%] and Clarity [%] are measured with a haze meter (Haze Guard II; manufactured by Toyo Seiki Seisakusho Co., Ltd.). did.

(3) Tensile test In accordance with JIS K7127-1999 and ISO527-3, a tensile test was performed with a tensile tester (Strograph API II; manufactured by Toyo Seiki Seisakusho Co., Ltd.), yield strength [MPa] and tensile modulus. [GPa] was measured.

１）含有量：ポリエチレンテレフタレート樹脂と末端修飾ポリエチレンテレフタレートから下記の基を除いた残部との合計１００質量部に対する下記の基の含有量

２）アニール処理：１８０℃ １分間
試験化合物 ａ：１，２−ベンズイソチアゾール−３（２Ｈ）−オン１，１−ジオキシドナトリウム塩
ｂ：モンタン酸ナトリウム塩（Ｃｌａｒｉａｎｔ社製品名；リコモントＮａＶ１０１）
ｃ：カルボン酸ナトリウム塩

1) Content: Content of the following groups with respect to a total of 100 parts by mass of the polyethylene terephthalate resin and the remainder obtained by removing the following groups from the terminal-modified polyethylene terephthalate.

2) Annealing treatment: 180 ° C. for 1 minute Test compound a: 1,2-benzisothiazol-3 (2H) -one 1,1-dioxide sodium salt b: montanic acid sodium salt (Clariant product name; Recommont NaV101)
c: Carboxylic acid sodium salt

  From the above Examples 1 and 2, it was confirmed that when the annealing treatment was performed on the test piece, the transparency was lowered and the use in the transparent application was limited.

  From Example 1, it was confirmed that the molded product of the present invention was excellent in transparency, less colored, and greatly improved in physical properties with respect to the compound containing no crystal nucleating agent in Comparative Example 1.

[Reference example] Confirmation test of terminal modification (polymer bound) of polyethylene terephthalate
In advance, 100 parts by mass of polyethylene terephthalate was mixed with 1 part by mass of 1,2-benzisothiazol-3 (2H) -one 1,1-dioxide sodium salt, and a twin-screw extruder (equipment: Nippon Steel Corporation). 10g of pellets obtained by granulation with TEX28V (manufactured by TEX28V, cylinder temperature 270 ° C, screw speed 200rpm), frozen with dry ice and ground, refluxed with 100ml of 95% ethanol aqueous solution for 24 hours, and contained in the pellets The extracted additive component was extracted into an aqueous ethanol solution and quantified by ion chromatography (DX320, manufactured by DIONEX), but 1,2-benzisothiazol-3 (2H) -one, 1-1-dioxide sodium salt Was not detected at all. The analysis conditions were as follows.
Column: Ionpac AS19, eluent: potassium hydroxide, suppressor; ASRS 4 mm, current 150 mA, temperature 35 ° C.

  The energy state of 1S orbital of nitrogen in the following pellets or compounds is confirmed by X-ray photoelectron spectroscopy spectrum by X-ray photoelectron spectroscopy (AXIS-ULTRA, manufactured by Shimadzu Kratos Co., Ltd., measurement conditions; X-ray source: Mg 15 kV, 15 mA). did. FIG. 1 shows PET containing no nucleating agent, FIG. 2 shows PET containing 1,2-benzisothiazol-3 (2H) -one 1,1-dioxide sodium salt 1%, and FIG. 3 shows 1,2-benzisothiazole. -3 (2H) -one 1,1-dioxide sodium salt 3% combined PET, FIG. 4 shows 1,2-benzisothiazol-3 (2H) -one 1,1-dioxide sodium salt 5% combined PET, FIG. 5 shows 1,2-benzisothiazol-3 (2H) -one 1,1-dioxide sodium salt, FIG. 6 shows N-ethyl alcohol-1,2-benzisothiazol-3 (2H) -one 1, 1 represents an X-ray photoelectron spectrum of 1-dioxide.

From FIG. 1, polyethylene terephthalate (PET) not having nitrogen does not have a peak. FIG. 5 is an X-ray photoelectron spectroscopic spectrum of 1,2-benzisothiazol-3 (2H) -one 1,1-dioxide sodium salt. From FIGS. Compared with the X-ray photoelectron spectrum when benzisothiazol-3 (2H) -one 1,1-dioxide sodium salt was blended, it was confirmed that the position of the peak was shifted.
FIG. 6 shows that the X-ray photoelectron spectrum of the N-ethyl alcohol-1,2-benzisothiazol-3 (2H) -one 1,1-dioxide compound is compared with that in FIG. The X-ray photoelectron spectroscopy spectra of FIGS. 2 to 4 are bound to the polyester resin with 1,2-benzisothiazol-3 (2H) -one 1,1-dioxide sodium salt. The result which shows that was obtained.

Claims (6)

A polyester resin composition containing (A) a polyester resin and (B) a terminal-modified polyethylene terephthalate,
The (B) terminal-modified polyethylene terephthalate is a group represented by the following general formula (1), or a polyethylene terephthalate whose terminal is modified with a group represented by the following general formula (1) and a carboxylic acid metal salt. A polyester resin composition characterized by that.

(In the formula, X represents a direct bond or an alkylene group having 1 to 12 carbon atoms.)   For the total of 100 parts by mass of the (A) polyester resin and the remainder of the (B) terminal-modified polyethylene terephthalate excluding the group represented by the general formula (1), the formula (1) The polyester resin composition according to claim 1, wherein the content of the group to be formed is 0.001 to 1 part by mass.   The polyester according to claim 1 or 2, wherein the (A) polyester resin is one or more polyester resins selected from the group consisting of polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate, polyethylene naphthalate, and polybutylene naphthalate. Resin composition.   The polyester resin composition according to any one of claims 1 to 3, wherein the metal carboxylate is a sodium carboxylate.   A molded product obtained by molding the polyester resin composition according to any one of claims 1 to 4.   A sheet obtained by sheet-molding the polyester resin composition according to any one of claims 1 to 4, wherein the sheet is not annealed.

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