KR20030046300A - Polyester resin composition and process for producing the same - Google Patents

Abstract

PURPOSE: Provided is a polyester resin composition having excellent impact resistance and flow properties. CONSTITUTION: The polyester resin composition comprises (A) 50-97 wt.% of a polyester resin; (B) 2-40 wt.% of an ethylene-alpha-olefin copolymer rubber and/or an ethylene-alpha-olefin-polyene copolymer rubber, whose crystal melting heat is 10 J/g or less, as measured according to JIS-K-7122 using a differential scanning calorimeter; and (C) 1-15 wt.% of an epoxy group-containing ethylene copolymer comprising ethylene units and epoxy group-containing monomer units, wherein (A)+(B)+(C)=100 wt.%. Preferably, the (A) component is a polyethyleneterephthalate resin. More particularly, the (A) component is ground PET bottles or re-pelletized PET bottles.

Description

Polyester resin composition and process for producing same

The present invention relates to a polyester resin composition excellent in impact resistance and fluidity. The present invention particularly relates to a polyester resin composition which exhibits excellent impact resistance and fluidity even when the polyester resin used to produce the polyester resin composition contains a regenerated polyester resin.

It is recommended to recycle and reuse a polyester resin container (hereinafter referred to as a "PET bottle") such as a polyethylene terephthalate container. However, the regenerated polyester resin has a problem that the impact resistance is lowered.

As a resin composition for solving this problem, JP-A-63-4566 discloses a resin composition composed of a polyester resin, an ethylene-α-olefin copolymer and an epoxy group-containing ethylene copolymer.

However, since the resin composition of the said publication has low fluidity | liquidity, there exists a problem that moldability falls.

An object of the present invention is to provide a polyester resin composition excellent in impact resistance and fluidity.

It is also an object of the present invention to provide a method for producing the polyester resin composition.

This invention relates to the polyester resin composition which consists of the following component (A), a component (B), and a component (C). Let total amount of a component (A), a component (B), and a component (C) be 100 weight%. ]:

Component (A): 50-97 weight% of polyester resin,

Component (B): Ethylene-alpha-olefin copolymer rubber, ethylene-alpha-olefin-polyene compound copolymer rubber whose crystal melting heat measured by the differential scanning calorimeter based on JIS-K-7122 is 10 J / g or less, or 2 to 40% by weight of a combination of these copolymer rubbers and

Component (C): 1-15 weight% of epoxy group containing copolymers containing an ethylene unit and an epoxy group containing monomeric unit.

This invention is a manufacturing method (henceforth "manufacturing method (1)") of the above-mentioned polyester resin composition including following process (1) and process (2).

Step (1): a step of melting and mixing all or part of component (B) with thermoplastic resin and / or component (C) to obtain masterbatch pellets, and

Process (2): The process of mixing a masterbatch pellet, component (A), and the remaining component (C) (when a part of component (C) is used in process (1)) to obtain a polyester resin composition.

This invention is a manufacturing method (henceforth "manufacturing method (2)") of the said polyester resin composition including the following process (1) and process (2) further.

Step (1): obtaining a multilayer pellet comprising component (B) as a core and seeding all or part of the thermoplastic resin and / or component (C); and

Process (2): The process of mixing a multilayer pellet, component (A), and remaining component (C) (when a part of component (C) is used in process (1)), and obtaining a polyester resin composition.

In the present invention, the term "ethylene unit" and similar terms have the meaning "weight unit of ethylene" and the like.

Embodiment of the invention

As a polyester resin of the component (A) used by this invention, the polycondensation product of diol and dicarboxylic acid can be illustrated. "Dicarboxylic acid" may also mean derivatives such as esters, acid anhydrides and halides of the dicarboxylic acids in addition to the free dicarboxylic acids.

Examples of the diol include carbon atoms of 2 to 20 carbon atoms such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,10-decanediol, and neopentyl glycol Chain or branched aliphatic diols; Diols containing alicyclic groups such as 1,4-cyclohexanediol and 1,4-cyclohexanediethanol; Long chain glycols such as polyethylene glycol, poly-1,3-propylene glycol and polytetramethylene glycol having a molecular weight of about 400 to 6000; And combinations of two or more of these diols.

As dicarboxylic acid, C2-C20 aliphatic dicarboxylic acid, such as azelaic acid, adipic acid, sebacic acid, and dodecane dicarboxylic acid; Aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, phthalic acid, bis (4-carboxyphenyl) methane, 1,2-bis (4-carboxyphenyl) ethane, 4,4'-dicarboxybiphenyl ether and naphthalenedicarboxylic acid; Dicarboxylic acid containing an alicyclic group such as cyclohexanedicarboxylic acid; Methyl esters, ethyl esters, acid anhydrides and halides of these dicarboxylic acids; And combinations of two or more of these dicarboxylic acids. Especially, as dicarboxylic acid, dicarboxylic acid containing 40 mol% or more of terephthalic acid is preferable.

As polyester resin, polyethylene terephthalate resin, polypropylene terephthalate resin, polybutylene terephthalate resin, polyhexamethylene terephthalate resin, polyethylene naphthalate resin, polybutylene naphthalate resin, polycyclohexanediethylene terephthalate resin, poly Neopentyl terephthalate resin and the combination of 2 or more types of these polyester resin can be illustrated.

Especially, polyethylene terephthalate; Polycondensates of a mixture of isophthalic acid and terephthalic acid with ethylene glycol; Polycondensates of a mixture of adipic acid and terephthalic acid with ethylene glycol; Polycondensates of a mixture of decandicarboxylic acid and terephthalic acid with ethylene glycol; Preferred are a polycondensation product of a mixture of ethylene glycol and propylene glycol and terephthalic acid and a condensation product of a mixture of ethylene glycol and butylene glycol and terephthalic acid. In particular, a polyester resin obtained from dicarboxylic acid containing at least about 80 mol% of terephthalic acid and diol containing at least 80 mol% of ethylene glycol is preferable.

As a polyester resin used for this invention, the polyester resin which consists of regenerated polyester resin is preferable. "Regenerated polyester resin" means the polyester resin which made the polyester resin composition (for example, PET bottle) after use into the shape of powder, a pulverized object, and pellets, etc. in order to reuse.

It is preferable that the intrinsic viscosity of a polyester resin is 0.5-1.0 dl / g normally at 25 degreeC using o-chlorophenol as a solvent. As for the terminal carboxyl group concentration of a polyester resin, 15-200 m equivalent / kg is preferable normally.

The heat of crystal melting of component (B) measured by differential scanning calorimeter (DSC) in accordance with JIS-K-7122 is 10 J / g or less, preferably 8 J / g or less, more preferably 5 J / g or less, further preferably Preferably 3 J / g or less. When the calorie value exceeds 10 J / g, the balance between impact resistance and fluidity of the obtained polyester resin composition is poor.

Examples of the α-olefins of the ethylene-α-olefin copolymer rubber of the component (B) or the ethylene-α-olefin-polyene compound copolymer rubber are propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1 -Octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene Linear α-olefins such as 1-nanodecene and 1-eicosene; And branched α such as 3-methyl-1-butene, 3-methyl-1-pentene, 4-methyl-1-pentene, 2-ethyl-1-hexene and 2,2,4-trimethyl-1-pentene -Olefin can be illustrated. Among them, linear α-olefins are preferable, and propylene, 1-butene, 1-pentene, 1-hexene, 1-octene or 1-decene are particularly suitable.

As a polyene compound of the ethylene-alpha-olefin-polyene compound copolymer rubber of component (B), the compound which has several double bonds, such as a conjugated polyene compound and a nonconjugated polyene compound, can be illustrated.

As a conjugated polyene compound, a linear aliphatic conjugated polyene compound, a branched aliphatic conjugated polyene compound, and an alicyclic conjugated polyene compound can be illustrated. The conjugated polyene compound may include a group such as an alkoxy group, an aryl group, an aryloxy group, an aralkyl group and an aralkyloxy group.

As the aliphatic conjugated polyene compound, 1,3-butadiene, isoprene, 2-ethyl-1,3-butadiene, 2-propyl-1,3-butadiene, 2-isopropyl-1,3-butadiene, 2-hexyl-1 , 3-butadiene, 2,3-dimethyl-1,3-butadiene, 2,3-diethyl-1,3-butadiene, 2-methyl-1,3-pentadiene, 2-methyl-1,3-hexa Dienes, 2-methyl-1,3-octadiene, 2-methyl-1,3-decadiene, 2,3-dimethyl-1,3-pentadiene, 2,3-dimethyl-1,3-hexadiene, 2,3-dimethyl-1,3-octadiene and 2,3-dimethyl-1,3-decadiene can be exemplified.

As the alicyclic conjugated polyene compound, 2-methyl-1,3-cyclopentadiene, 2-methyl-1,3-cyclohexadiene, 2,3-dimethyl-1,3-cyclopentadiene, 2,3-dimethyl -1,3-cyclohexadiene, 2-chloro-1,3-butadiene, 2,3-dichloro-1,3-butadiene, 1-fluoro-1,3-butadiene, 2-chloro-1,3- Pentadiene, 2-chloro-1,3-cyclopentadiene and 2-chloro-1,3-cyclohexadiene can be exemplified.

Examples of the nonconjugated polyene compound include linear aliphatic nonconjugated polyene compounds, branched aliphatic nonconjugated polyene compounds, alicyclic nonconjugated polyene compounds, and aromatic nonconjugated polyene compounds. The nonconjugated polyene compound may include a group such as an alkoxy group, an aryl group, an aryloxy group, an aralkyl group, an aralkyloxy group, or the like.

Examples of the aliphatic nonconjugated polyene compounds include 1,4-hexadiene, 1,5-hexadiene, 1,6-heptadiene, 1,6-octadiene, 1,7-octadiene, 1,8-nonadiene, 1 , 9-decadiene, 1,13-tetradecadiene, 1,5,9-decatene, 3-methyl-1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl- 1,4-hexadiene, 4-ethyl-1,4-hexadiene, 3-methyl-1,5-hexadiene, 3,3-dimethyl-1,4-hexadiene, 3,4-dimethyl-1, 5-hexadiene, 5-methyl-1,4-heptadiene, 5-ethyl-1,4-heptadiene, 5-methyl-1,5-heptadiene, 6-methyl-1,5-heptadiene, 5 -Ethyl-1,5-heptadiene, 3-methyl-1,6-heptadiene, 4-methyl-1,6-heptadiene, 4,4-dimethyl-1,6-heptadiene, 4-ethyl-1 , 6-heptadiene, 4-methyl-1,4-octadiene, 5-methyl-1,4-octadiene, 4-ethyl-1,4-octadiene, 5-ethyl-1,4-octadiene, 5-methyl-1,5-octadiene, 6-methyl-1,5-octadiene, 5-ethyl-1,5-octadiene, 6-ethyl-1,5-octadiene, 6-methyl-1, 6-octadiene, 7-methyl-1,6-octadiene, 6-ethyl-1,6-octadiene, 6-propyl-1,6-octadiene, 6-butyl-1,6-octadiene, 4-methyl-1,4-nonadiene, 5-methyl-1,4-nonadiene, 4-ethyl-1,4-nonadiene, 5-ethyl-1, 4-nonadiene, 5-methyl-1,5-nonadiene, 6-methyl-1,5-nonadiene, 5-ethyl-1,5-nonadiene, 6-ethyl-1,5-nonadiene, 6 -Methyl-1,6-nonadiene, 7-methyl-1,6-nonadiene, 6-ethyl-1,6-nonadiene, 7-ethyl-1,6-nonadiene, 7-methyl-1,7 -Nonadiene, 8-methyl-1,7-nonadiene, 7-ethyl-1,7-nonadiene, 5-methyl-1,4-decadiene, 5-ethyl-1,4-decadiene, 5- Methyl-1,5-decadiene, 6-methyl-1,5-decadiene, 5-ethyl-1,5-decadiene, 6-ethyl-1,5-decadiene, 6-methyl-1,6- Decadiene, 6-ethyl-1,6-decadiene, 7-methyl-1,6-decadiene, 7-ethyl-1,6-decadiene, 7-methyl-1,7-decadiene, 8-methyl -1,7-decadiene, 7-ethyl-1,7-decadiene, 8-ethyl-1,7-decadiene, 8-methyl-1,8-decadiene, 9-methyl-1,8-deca Diene, 8-ethyl-1,8-decadiene, 6-methyl-1,6-undecadiene, 9-methyl-1,8-undecadiene, 6,10-dimethyl-1,5,9-unde Katrien, 5,9-D Tyl-1,4,8-decatriene, 4-ethylidene-8-methyl-1,7-nonadiene, 13-ethyl-9-methyl-1,9,12-pentadecethylene, 5,9 , 13-trimethyl-1,4,8,12-tetradecadiene, 8,14,16-trimethyl-1,7,14-hexadecatene and 4-ethylidene-12-methyl-1,11-penta Decadiene can be illustrated.

Examples of the alicyclic nonconjugated polyene compound include vinylcyclohexene, 5-vinyl-2-norbornene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, and 5-isopropenyl-2. Norbornene, cyclohexadiene, dicyclopentadiene, cyclooctadiene, 2,5-norbornadiene, 2-methyl-2,5-norbornadiene, 2-ethyl-2,5-norborne Nadiene, 2,3-Diisopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene-5-norbornene, 6-chloromethyl-5-isopropenyl-2-norbornene 1,4-divinylcyclohexane, 1,3-divinylcyclohexane, 1,3-divinylcyclopentane, 1,5-divinylcyclooctane, 1-aryl-4-vinylcyclohexane, 1, 4-diarylcyclohexane, 1-aryl-5-vinylcyclooctane, 1,5-diarylcyclooctane, 1-aryl-4-isopropenylcyclohexane, 1-isopropenyl-4-vinylcyclohexane, 1-isopropenyl-3-vinylcyclopentane and methyltetrahydrate There may be mentioned indene.

When component (B) is an ethylene-alpha-olefin copolymer rubber, it is preferable that the molar ratio of the ethylene unit / alpha-olefin unit in the said component is 5 / 95-70 / 30 normally.

When component (B) is an ethylene-alpha-olefin-polyene compound copolymer rubber, the molar ratio of the ethylene unit / alpha-olefin unit in the said component is 5 / 95-70 / 30 normally, and the urea value of this component is 1-100. It is preferable that it is (g / 100g- glycol copolymer rubber).

The melt flow rate (MFR) at 190 ° C. and 2.16 kg (load) of component (B), measured in accordance with JIS-K-7210, is preferably 1 to 100 g / 10 minutes, more preferably 0.5 To 20 g / 10 min. When MFR is less than 1 g / 10min, the fluidity | liquidity of the polyester resin composition obtained tends to fall. When MFR exceeds 100 g / 10min, there exists a tendency for the mechanical properties (for example, impact strength) of the polyester resin composition obtained to fall.

As a manufacturing method of component (B), the well-known method of polymerizing a monomer in presence of polymerization catalysts, such as a Ziegler-Natta type catalyst or a metallocene type catalyst, can be illustrated. Examples of the metallocene catalyst include transition metal complexes of Groups 4A to 6A of the periodic table having at least one cyclopentadienyl skeleton. As a specific metallocene catalyst, the metallocene catalyst of Unexamined-Japanese-Patent No. 9-12635 or Unexamined-Japanese-Patent No. 9-151205 can be illustrated.

It is preferable that component (C) contains 70 to 99 weight% of ethylene units and 1 to 30 weight% of an epoxy group containing monomeric unit (the total amount of an ethylene unit and an epoxy group containing monomeric unit shall be 100 weight%).

When component (C) further comprises ethylenically unsaturated ester compound units, the component comprises 20 to 98% by weight ethylene units, 1 to 30% by weight epoxy group containing monomer units and 1 to 50% ethylenically unsaturated ester compound units It is preferable to contain% (the total amount of an ethylene unit, an epoxy group containing monomeric unit, and an ethylenically unsaturated ester compound unit shall be 100 weight%).

As an epoxy group containing monomer, the compound represented by following General formula (1) can be illustrated. In the formula, R represents an alkenyl group having 2 to 18 carbon atoms, and X represents a carbonyloxy group, methyleneoxy group or phenyleneoxy group.

In the compound represented by the formula (1), an unsaturated carboxylic acid glycidyl ester in which X is a carbonyloxy group, or an unsaturated carboxylic acid glycidyl ether in which X is a methyleneoxy group is preferable.

As unsaturated carboxylic acid glycidyl ester, glycidyl acrylate, glycidyl methacrylate, and itaconic acid glycidyl ester can be illustrated. As the unsaturated carboxylic acid glycidyl ether, arylglycidyl ether, metaarylglycidyl ether and styrene-p-glycidyl ether can be exemplified.

The ethylenically unsaturated ester compound is a compound containing no glycidyl ester group. As such a compound, Saturated carboxylic acid vinyl esters, such as vinyl acetate, a vinyl propionate, and a vinyl lactate; And unsaturated carboxylic acid alkyl esters such as methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate and butyl methacrylate. Especially, vinyl acetate, methyl acrylate, ethyl acrylate, or methyl methacrylate is preferable.

Component (C) may be any of a block copolymer, a graft copolymer, a random copolymer and an alternating copolymer. The copolymer may be, for example, a copolymer obtained by grafting an epoxy group-containing compound to a propylene-ethylene block copolymer (see Japanese Patent Publication No. 6252980), or an ethylenically unsaturated monomer in a copolymer of ethylene and an epoxy group-containing monomer. It may be a copolymer obtained by grafting an ester compound (see Japanese Patent Publication No. 2600248).

The MFR at 190 ° C and 2.16 kg (load) of component (C), measured in accordance with JIS-K-7210, is preferably 0.5 to 100 g / 10 minutes, more preferably 2 to 50 g / 10 minutes. When MFR is less than 0.5 g / 10min, there exists a tendency for the fluidity | liquidity of the obtained polyester resin composition to fall. When MFR exceeds 100 g / 10min, there exists a tendency for the mechanical properties (for example, impact strength) of the obtained polyester resin composition to fall.

The number average molecular weight of component (C) measured by gel permeation chromatography (GPC) is preferably 10,000 to 100,000 in terms of the number average molecular weight of polystyrene. When this molecular weight is less than 10,000, there exists a tendency for the mechanical physical property (for example, impact strength) of the obtained polyester resin composition to fall. When the said molecular weight exceeds 100,000, there exists a tendency for the fluidity | liquidity of the obtained polyester resin composition to fall.

As a method for producing component (C), (1) a method of copolymerizing monomers at 50 to 400 MPa and 100 to 300 ° C in the presence or absence of a suitable solvent or chain transfer agent in the presence of a radical generator or (2) polyethylene, Epoxy group-containing monomers, radical generators and optionally ethylenically unsaturated esters may be mixed to melt graft copolymerize in an extruder.

The polyester resin composition of the present invention or the polyester resin composition obtained by the production method of the present invention is 50 to 97% by weight of component (A), preferably 60 to 95% by weight, and 2 to 40% by weight of component (B). , Preferably 3 to 35% by weight, component (C) 1 to 15% by weight, preferably 2 to 10% by weight (the total amount of component (A), component (B) and component (C) is 100 Weight percent).

If component (A) is less than 50 weight%, the fluidity | liquidity or rigidity of the obtained polyester resin composition will fall. When component (A) exceeds 97 weight%, the impact strength of the obtained polyester resin composition falls. When component (B) is less than 2 weight%, the impact strength of the obtained polyester resin composition falls. When component (B) exceeds 40 weight%, the heat resistance of the obtained polyester resin composition falls. When component (C) is less than 1 weight%, the impact strength of the obtained polyester resin composition falls. When component (C) exceeds 15 weight%, the fluidity | liquidity of the obtained polyester resin composition will fall.

As for MFR (melt flow rate) of 190 degreeC and 2.16 kg (load) of the polyester resin composition of this invention measured based on JIS-K-7210, 40-300 g / 10min is preferable normally. If this MFR is less than 40 g / 10 minutes, since the melt viscosity of the said composition rises, it exists in the tendency for the shaping | molding by a large injection molding machine to become difficult. When the MFR exceeds 300 g / 10 min, handling of the composition tends to be difficult.

Each component used to prepare the polyester resin composition of the present invention is a conventional compounding agent for resins such as heat stabilizers, antioxidants, weathering agents, light stabilizers, nucleating agents, lubricants, mold release agents, pigments, flame retardants, antistatic agents and fillers Or a reinforcing agent such as glass fiber or other thermoplastic resin such as polyethylene and polypropylene.

As a manufacturing method of the polyester resin composition of this invention, the following manufacturing methods ①-④ can be illustrated.

Manufacturing Method ①

Process (1): The process of melt-mixing all or part of component (B) with a thermoplastic resin and / or component (C) to obtain a masterbatch pellet.

Process (2): The process of mixing the said masterbatch pellet, component (A), and the remaining component (C) (when using a part of component (C) in process (1)), and obtaining a polyester resin composition.

Manufacturing Method ②

Process (1): The process of obtaining the multilayer pellet which makes component (B) the core and seeds the whole or part of thermoplastic resin and / or component (C).

Process (2): The process of mixing the said multilayer pellet, component (A), and remaining component (C) (when a part of component (C) is used in process (1)) and obtaining a polyester resin composition.

Manufacturing Method ③

Process (1): The process of dry-compounding a component (A), a component (B), and a component (C).

Process (2): The process of melt-kneading the said compound in apparatuses, such as a single screw or twin screw extruder, a Banbury mixer, a roll, and a kneader.

Manufacturing Method ④

Process (1): The process of dry-compounding a component (A), a component (B), and a component (C).

Process (2): The process of injection molding the said compound.

The preferable manufacturing method of the polyester resin composition of this invention is said manufacturing method (1) or (2).

Manufacturing methods ① and ② are suitable methods for pelletizing low crystallinity component (B). In the process (1) of the manufacturing method ①, the preferable compounding ratio of component (B) and a thermoplastic resin is 50/50-90/10 (weight part). If the component (B) exceeds 90 parts by weight, the obtained masterbatch pellets may adhere to each other during storage, and as a result, they may become unusable. When component (B) is less than 50 weight part, the impact strength of the obtained polyester resin composition may fall.

Manufacturing method ② is a method suitable for pelletizing component (B) using a small amount of thermoplastic resin. The multilayer pellets obtained in step (1) of this manufacturing method do not adhere well to each other during storage. In the step (1), the preferred blending ratio of component (B) and the thermoplastic resin is 50/50 to 99/1 (parts by weight). When component (B) exceeds 99 weight part, the multilayer pellets obtained may adhere | attach with each other during storage, and may become unusable as a result. When component (B) is less than 50 weight part, the impact strength of the obtained polyester resin composition may fall.

As a preferable thermoplastic resin used by the manufacturing method (1) or (2), Polyolefin resin, such as polyethylene or a polypropylene; Component (A) and component (C) can be illustrated. Especially, polyolefin resin or component (C), such as polyethylene or a polypropylene, is more preferable, and a component (C) is especially preferable. In the case of using component (C) as the thermoplastic resin in step (1) of the production method (1) or (2), when (a) using a small amount of component (C), the component (A) and component (C) are It is good to use, and (ii) When using a sufficient amount of component (C), it is not necessary to use component (C) in a process (2).

The multilayer pellet in the said manufacturing method (2) can be manufactured by the method of Unexamined-Japanese-Patent No. 2001-198918 (corresponding application is EP1063070A2, for example).

The polyester resin composition of the present invention or the polyester resin composition obtained in the production method of the present invention is used for vehicle parts, electrical and electronic device parts, electric wires, building materials, agricultural products, fishery products, horticultural products, chemical industrial products, civil engineering materials. It can be used for industrial and industrial materials, furniture, stationery, daily necessities, sundries, garments, containers, packaging, toys, leisure and medical supplies. Specific uses include electrical and electronic parts such as a cover for a motor or a cover for a bulb socket; Automotive parts such as injection coil covers, engine covers and foil covers; Civil engineering and housing-related building materials such as window sash; Household goods such as hangers, chairs and trash cans; Stationery, such as binders, notebooks, covers, files, and book holders; Packaging products such as garbage bags; and the like. Especially, it is suitable for the molded object (especially large molded object) in which physical properties, such as dustproofness or impact resistance, are calculated | required.

Example

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

Examples 1 and 2, Comparative Examples 1 to 3

As a component (A), the polyester resin which grind | pulverized and recycled the recycling bottle called the recycling pet resin (brand name) by the Utsumi Kikakusha company is used.

As component (B), ethylene-propylene copolymer rubber (mooney viscosity ML _{1 + 4} (100 ° C.) = 43, content of propylene unit = 53 wt%, crystal melting calorie measured in accordance with JIS-K-7122) Is not detected).

As the component (C), an epoxy group-containing ethylene copolymer (content of glycidyl methacrylate unit = 12% by weight and MFR (190 ° C, 2.16 kg)), called Bond Fast E (brand name) manufactured by Sumitomo Chemical Industries, Ltd. 3 g / 10 min).

As other components, ESPREN SPO V0111 (trade name) ethylene-propylene copolymer (content of the propylene unit = 22 weight%, MFR (190 degreeC, 2.16 kg) = 0.9 g / 10min) and JIS-K by Sumitomo Chemical Co., Ltd. Calorie melting amount = 54 J / g) measured according to -7122.

1. Preparation of two-layer pellets

The component (B) was crushed into a chip in a pulverizer, and the pulverized product was mixed with 1 phr of powdered polyethylene (anti-adhesive inhibitor) manufactured by Sumitomo Seikasha Co. L / D = 35).

On the other hand, the random polypropylene (MFR = 8 at 230 degreeC) of Sumitomo Chemical Co., Ltd. product name Sumitomo Noblen W531 is supplied to the single screw extruder (diameter = 40 mm, L / D = 25) for seed.

Each component supplied to the two extruders is fed to a core-seed die (6 diameters) at a feed ratio of core and seed = 95/5 (weight ratio) at 240 ° C.

Six strands extruded from the die were passed through a water bath and cooled, and then cut with a pelletizer to obtain a two-layer pellet having a core-seed structure having an outer diameter of 4.0 mm, a length of 4.0 mm, and a seed thickness of 0.06 mm. 2000 ppm of prosene UF4 (anti-adhesion inhibitor) is applied to the pellet.

2. Polyester Resin Composition

After dry blending each component at the blending ratio shown in Table 1, the blend was fed to a coaxial twin screw extruder (diameter = 30 mm, L / D = 42) to give a screw speed of 200 rpm and a feed rate of 18 kg / hour. The melt kneading at 290 ℃ to obtain a pellet-like composition.

After drying the composition for 4 hours in a dehumidifying dryer (150 ° C.), the melt flow rate (290 ° C., 2.16 kg load) of the dried composition is measured according to JIS-K-7210. The results are shown in Table 1.

The dried composition is injection molded at a molding temperature of 280 ° C. and a mold temperature of 60 ° C. to prepare a test piece, and to measure the Izod impact strength according to ASTM-D256 and the flexural modulus according to JIS-K-7203. The results are shown in Table 1.

Example Comparative example One 2 One 2 3 Compounding ratio (% by weight) Component (A) Component (B) Component (C) Other components 85123- 9082- 85-312 90-28 100 --- MFR (290 ° C, g / 10min) 125 135 131 181 222 Impact Strength (-20 ℃, kJ / m ² ) 7.2 4.8 6.0 4.0 2.5 Flexural Modulus (MPa) 1624 1863 1605 1868 2382

The polyester resin composition of the present invention exhibits excellent impact resistance and fluidity, and particularly exhibits excellent impact resistance and fluidity even when the polyester resin used to prepare the polyester resin composition of the present invention contains a regenerated polyester resin. .

Claims (8)

The polyester resin composition consisting of the following component (A), a component (B), and a component (C) is made into 100 weight% of the total amount of a component (A), a component (B), and a component (C). Component (A): 50-97 weight% of polyester resin, Component (B): Ethylene-alpha-olefin copolymer rubber, ethylene-alpha-olefin-polyene compound copolymer rubber whose crystal melting heat measured by the differential scanning calorimeter based on JIS-K-7122 is 10 J / g or less, or 2 to 40% by weight of a combination of these copolymer rubbers and Component (C): 1-15 weight% of epoxy group containing copolymers containing an ethylene unit and an epoxy group containing monomeric unit. The polyester resin composition of Claim 1 in which component (A) consists of a polyethylene terephthalate resin. The polyester resin composition of Claim 1 in which a component (A) consists of a regenerated polyester resin. The polyester resin composition according to claim 1, wherein the component (A) is made of a pulverized product of a polyethylene terephthalate resin container or a repellet product of a polyethylene terephthalate resin bottle. The polyester resin composition according to claim 1, wherein the component (C) contains 70 to 99% by weight of ethylene units and 1 to 30% by weight of epoxy group-containing monomer units (the total amount of ethylene units and epoxy group-containing monomer units is 100% by weight. %). The polyester resin composition according to claim 1, wherein component (C) comprises 20 to 98% by weight of ethylene units, 1 to 30% by weight of epoxy group-containing monomer units, and 1 to 50% by weight of ethylenically unsaturated ester units (ethylene units , The total amount of the epoxy group-containing monomer unit and the ethylenically unsaturated ester unit is 100% by weight). The manufacturing method of the polyester resin composition of Claim 1 containing following process (1) and process (2). Step (1): a step of melting and mixing all or part of component (B) with thermoplastic resin and / or component (C) to obtain masterbatch pellets, and Process (2): The process of mixing a masterbatch pellet, component (A), and the remaining component (C) (when a part of component (C) is used in process (1)) to obtain a polyester resin composition. The manufacturing method of the polyester resin composition of Claim 1 containing following process (1) and process (2). Step (1): obtaining a multilayer pellet comprising component (B) as a core and seeding all or part of the thermoplastic resin and / or component (C); and Process (2): The process of mixing a multilayer pellet, component (A), and remaining component (C) (when a part of component (C) is used in process (1)), and obtaining a polyester resin composition.