JP2002212406A - Resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyester resin composition excellent in both impact resistance and flowability. SOLUTION: In the polyester resin composition comprising (A) a polyester resin, (B) a copolymer of ethylene with an ethylenic unsaturated ester compound and (C) an epoxy group-containing ethylene copolymer, where the amounts (in pts.wt.) of the components (A) to (C) are such that the amount of the component (B) is 1-50 pts.wt. and the amount of the component (C) is 1-12 pts.wt., both based on 100 pts.wt. of the component (A), S represented by the formula: S=10.4×ln[(B)]+44.2×ln[(C)] ([(B)] and [(C)] are each the amount in pts.wt., based on 100 pts.wt. of the component (A), of the components (B) and (C), respectively) is 20-110 and the total weight of the components (B) and (C) is at least 6 pts.wt. based on 100 pts.wt. of the component (A).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a polyester resin composition. Specifically, (A) polyester resin,
The present invention relates to a polyester resin composition comprising (B) a copolymer of ethylene and an ethylenically unsaturated ester compound, and (C) an epoxy group-containing ethylene copolymer having excellent impact resistance and fluidity.

[0002]

2. Description of the Related Art In recent years, containers made of polyester resin such as polyethylene terephthalate have been widely used for PET bottles and the like, and recycling (reuse) of the collected products has been demanded. There is a problem that the polyester resin is deteriorated by heat once molded, or the impact resistance is reduced when molded again. In order to solve this problem, a method has been proposed in which a polyester resin contains a copolymer of ethylene and an ethylenically unsaturated ester compound, and an ethylene copolymer containing an epoxy group (for example, Japanese Patent Application Laid-Open (JP-A) No. Hei 9 (1999)). 10-152607, JP-A-11-255906).

[0003]

However, based on Japanese Patent Application Laid-Open No. H10-152607, the present inventors reported that 100 parts by weight of polyethylene terephthalate, 23.5 parts by weight of a copolymer of ethylene and methyl acrylate, and Examination of a resin composition obtained by melt-kneading 5.8 parts by weight of a glycidyl methacrylate-methyl acrylate copolymer reveals that the fluidity of the composition is low. When the composition is molded by a large injection molding machine or the like having an injection volume of 1500 cm ³ or more, a so-called short shot occurs,
Molding proved difficult. Further, the present inventors based on JP-A-11-255906,
A resin composition was prepared by melt-kneading 100 parts by weight of polyethylene terephthalate, 1.1 parts by weight of a copolymer of ethylene and methyl acrylate, and 4.2 parts by weight of a copolymer of ethylene, glycidyl methacrylate and methyl acrylate. Then, it became clear that the impact resistance was not sufficient. An object of the present invention is to provide a polyester resin composition excellent in both impact resistance and fluidity.

[0004]

In order to solve the above problems, (A) a polyester resin, (B) a copolymer of ethylene and an ethylenically unsaturated ester compound, and (C) an epoxy group-containing ethylene copolymer After extensive studies on the polyester resin composition containing the coalesced,
By containing the components (B) and (C) in a specific amount or more and adjusting the weight ratio of the two components to a specific value, the resulting polyester resin composition can be used in any of impact resistance and fluidity. Furthermore, it has been found that even a polyester resin composition containing a pulverized PET bottle in which the component (A) has been molded once, the resin composition has excellent impact resistance and fluidity. Thus, the present invention has been completed.

That is, the present invention comprises (A) a polyester resin, (B) a copolymer of ethylene and an ethylenically unsaturated ester compound, and (C) an epoxy group-containing ethylene copolymer. The content (parts by weight) of component (C) is 100 parts of component (A), and the amount of component (B) 1
In the polyester resin composition comprising 50 parts to 50 parts and 1 to 12 parts of the component (C), the following formula (1) S = 10.4 × ln [(B)] + 44.2 × ln [(C)] (1) (Wherein [(B)] and [(C)] are (A)
It represents the content (parts by weight) of the components (B) and (C) based on 100 parts of the component. ) Is 20 to 110
And the total weight of the components (B) and (C) is (A)
The polyester resin composition is characterized in that the amount is 6 parts or more based on 100 parts of the component.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. Examples of the polyester resin as the component (A) in the present invention include a condensation polymer of a diol and a dicarboxylic acid. Here, as the diol, for example, ethylene glycol, 1,3-propanediol, 1,4-
Linear or branched aliphatic diols having about 2 to 20 carbon atoms, such as butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,10-decanediol, and neopentyl glycol; Cyclohexanediol, diol containing an alicyclic group such as 1,4-cyclohexanediethanol, polyethylene glycol having a molecular weight of about 400 to 6000, poly-1,
Long-chain glycols such as 3-propylene glycol and polytetramethylene glycol are exemplified. Two or more diols may be used as the diol.

The dicarboxylic acids include, for example,
Azelaic acid, adipic acid, sebacic acid, aliphatic dicarboxylic acids having about 2 to 20 carbon atoms such as dodecanedicarboxylic 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 ,
Examples thereof include dicarboxylic acids containing an alicyclic group such as cyclohexanedicarboxylic acid, methyl or ethyl esters of dicarboxylic acids, dicarboxylic anhydrides, and dicarboxylic acid halides. As the dicarboxylic acids, two or more dicarboxylic acids may be used. Among them, it is preferable to use dicarboxylic acids containing about 40 mol% or more of terephthalic acid.

Specific examples of component (A) include polyethylene terephthalate resin, polypropylene terephthalate resin, polybutylene terephthalate resin, polyhexamethylene terephthalate resin, polyethylene naphthalate resin, polybutylene naphthalate resin, polycyclohexanediethylene terephthalate resin, and polycyclohexanediethylene terephthalate resin. And neopentyl terephthalate resin. The component (A) may be a mixture of two or more polyester resins.

Among the components (A), for example, polyethylene terephthalate, a condensation polymer of a mixture of isophthalic acid and terephthalic acid and ethylene glycol, a condensation polymer of a mixture of adipic acid and terephthalic acid and ethylene glycol, decanedicarboxylic acid Polyethylene terephthalate resins such as polycondensates of terephthalic acid with ethylene glycol, terephthalic acid with ethylene glycol and propylene glycol, and terephthalic acid with ethylene glycol and butylene Preferably, about 80 mol% or more of the dicarboxylic acid component is terephthalic acid, and about
A polyethylene terephthalate resin whose main component is polyethylene terephthalate in which 80 mol% or more is ethylene glycol is preferred.

As the component (A), a recovered polyester resin molded at least once into a PET bottle or the like may be used, and examples of the shape of the resin include powder, pulverized product, and pellet product. Further, a melt-kneaded product of the recovered polyester resin or a repellet product thereof may be used as the component (A). The intrinsic viscosity of the component (A) is usually 0.5 to 25 ° C. using O-chlorophenol as a solvent.
It is about 1.0 dl / g. The concentration of the terminal carboxyl group of the component (A) is usually about 15 to 200 meq / Kg.

The component (B) in the present invention is usually a copolymer of ethylene and an ethylenically unsaturated ester compound, and among them, 100% by weight of all monomer units constituting the component (B). On the other hand, ethylene unit 50 ~
A copolymer containing about 99% by weight and about 1 to 50% by weight of an ethylenically unsaturated ester compound unit is preferred.

Here, the ethylenically unsaturated ester compound is a compound having an ester group other than glycidyl ester and an unsaturated hydrocarbon group copolymerizable with ethylene, and specific examples thereof include vinyl acetate and vinyl propionate. , Vinyl esters of saturated carboxylic acids such as vinyl butyrate,
Examples include alkyl esters of unsaturated carboxylic acids such as methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, and butyl methacrylate. Among them, vinyl acetate, methyl acrylate, ethyl acrylate, methyl methacrylate and the like are preferable.

In the present invention, the component (B) can be produced, for example, by reacting a monomer in the presence of a radical generator.
A method of copolymerizing in the presence or absence of a suitable solvent or chain transfer agent at about 500 to 4000 atm, about 100 to 300 ° C, mixing polyethylene with an ethylenically unsaturated ester compound, a radical generator, etc., and extruding And a method of performing melt graft copolymerization in an apparatus.

As the component (B) of the present invention, for example, Evatate, Smitate, Acrif (above, manufactured by Sumitomo Chemical Co., Ltd.), Ultracene (manufactured by Tosoh Corporation), Jerex EVA (manufactured by Japan Polyolefin Co., Ltd.) ), Mirason E
VA (manufactured by Mitsui Chemicals, Inc.), Evaflex, Nuclel, Evaflex EEA (all manufactured by Mitsui / Dupont Polychemicals), Primacol (manufactured by Dow Chemical), EMAC (manufactured by Nagase & Co., Ltd.) And a copolymer of ethylene and an ethylenically unsaturated ester compound which is commercially available under a registered trademark such as NUC EEA copolymer (manufactured by Nippon Unicar Co., Ltd.).

The epoxy group-containing ethylene copolymer (C) in the present invention is generally a copolymer of ethylene, an epoxy group-containing monomer unit and an ethylenically unsaturated ester compound. Above all, ethylene units of 20 to 99 per 100% by weight of all monomer units constituting component (C) are used.
About 1% by weight, epoxy group-containing monomer unit 1 to 30% by weight
Degree, and ethylenically unsaturated ester compound unit 1 to 50
It is preferable that the copolymer contains about% by weight.
In particular, the ethylenically unsaturated ester compound unit is 3 to 5
The copolymer preferably contains about 0% by weight, more preferably about 10 to 50% by weight.
When the weight ratio of the ethylenically unsaturated ester compound unit in the component (C) is less than 1% by weight, the impact resistance of the obtained resin composition tends to decrease, which is not preferable.

Here, the epoxy group-containing monomer used as the monomer of the component (C) includes, for example, the following general formula (2) (Wherein, R represents an alkenyl group having 2 to 18 carbon atoms, and X represents a carbonyloxy group, a methyleneoxy group or a phenyleneoxy group).

Of the above general formula (2), an unsaturated carboxylic acid glycidyl ester unit in which X is a carbonyloxy group and an unsaturated carboxylic acid glycidyl ether unit in which X is a methyleneoxy group are preferred. As the unsaturated carboxylic acid glycidyl ester, for example, glycidyl acrylate, glycidyl methacrylate, itaconic acid glycidyl ester and the like, and as the unsaturated glycidyl ether, for example, allyl glycidyl ether, methallyl glycidyl ether, styrene-p-glycidyl ether And the like.

The ethylenically unsaturated ester compound used as the monomer of the component (C) is the same compound as the ethylenically unsaturated ester compound used for the component (B).

The component (C) of the present invention may be any of a block copolymer, a graft copolymer, a random copolymer and an alternating copolymer. For example, propylene-ethylene described in Japanese Patent No. 6232980 may be used. A copolymer obtained by grafting an epoxy group-containing monomer onto a block copolymer, Patent No.
A copolymer obtained by grafting an ethylenically unsaturated ester compound to an ethylene / epoxy group-containing monomer copolymer described in JP-A-2600248 may be used.

The component (C) has an MFR (melt flow rate) measured according to JIS K7210 of 190 ° C.
The weight is preferably about 0.5 to 100 g / 10 minutes at 2.16 kg, and particularly preferably about 2 to 50 g / 10 minutes. If the MFR is less than 0.5 g / 10 minutes, the moldability of the obtained polyester composition tends to decrease. If it exceeds 100 g / 10 minutes, the mechanical properties of the resulting polyester composition, such as Izod impact strength, tend to decrease. The component (C) preferably has a number average molecular weight of about 10,000 to 100,000 in terms of polystyrene as measured by gel-vapor chromatography (GPC). When the molecular weight is less than 10,000, the mechanical properties of the obtained polyester composition, for example, the Izod impact strength tends to decrease, and when it exceeds 100,000, the moldability of the obtained polyester composition tends to decrease. Is not preferred.

As the method for producing the component (C), for example,
As described in JP-A-48-11388, a monomer is prepared in the presence of a radical generator at about 500 to 4,000 atm.
A method of copolymerizing in the presence or absence of a suitable solvent or a chain transfer agent at about 300 ° C. or less; mixing an epoxy group-containing monomer, an ethylenically unsaturated ester, a radical generator, etc. with polyethylene, and extruding the mixture in an extruder. Examples of the method include melt graft copolymerization.

The components (A), (B) and (C) thus obtained were mixed with 1 to 50 parts of the component (B) and 1 to 50 parts (by weight) based on 100 parts (by weight) of the component (A). In the polyester resin composition which is 〜12 parts, the following formula (1) S = 10.4 × ln [(B)] + 44.2 × ln [(C)] (1) (where [(B)] And [(C)] are, respectively, (A)
It represents the content (parts by weight) of the components (B) and (C) based on 100 parts of the component. ) Is 20 to 110
And the total weight of the components (B) and (C) is (A)
The resin composition blended so as to be at least 6 parts with respect to 100 parts of the component is the polyester resin composition of the present invention.

S is from 20 to 110, preferably 30
About 110. If S exceeds 110, the fluidity tends to decrease, which is not preferable. If it is less than 20, the impact resistance tends to decrease, and the molded article tends to crack, which is not preferable. In addition, the total weight of the components (B) and (C) is usually 10 (A).
The amount is 6 parts or more, preferably about 8 parts to 50 parts with respect to 0 parts. If the total weight of the components (B) and (C) is less than 6 parts, the impact resistance tends to decrease, which is not preferable.

MFR of the polyester resin composition of the present invention
(Melt flow rate) is usually about 40 to 300 g /
10 minutes (290 ° C, 2.16 kg, JIS K7210
And preferably 50 to 200 g / 10 min. If the MFR is less than 40, the melt viscosity increases, and molding with a large-sized injection molding machine tends to be difficult. If the MFR exceeds 300, handling of the resin composition tends to be difficult, which is not preferable. Further, the polyester resin composition of the present invention has a number average molecular weight in terms of polystyrene of 10,000 to 100,000 as measured by gel-power chromatography (GPC).
It is preferred that it is about. When the number average molecular weight is less than 10,000, the mechanical properties of the obtained polyester resin composition, for example, the Izod impact strength tends to decrease, and when it exceeds 100,000, the moldability of the obtained polyester resin composition Tends to decrease.

In the polyester resin composition of the present invention, if necessary, other compounding agents used in the polyester resin, for example, heat stabilizers, antioxidants, weathering agents, light stabilizers, nucleating agents, lubricants , Release agent, pigment, flame retardant, antistatic agent,
It may contain a filler and a reinforcing agent such as glass fiber. Further, other thermoplastic resins such as polyethylene and polypropylene may be blended as long as the object of the present invention is not impaired.

As a method for producing the polyester resin composition of the present invention, for example, after the components (A) to (C) are dry-blended, a single-screw or twin-screw extruder may be used.
A method of melt-kneading with a Banbury mixer, a roll, various kneaders or the like; a method of dry-blending and directly injection-molding; melt-kneading the components (B) and (C) in advance to form pellets; Melt kneading method;
A method in which at least one component selected from the components (A) to (C) and a thermoplastic resin are melt-kneaded into pellets, and then melt-kneaded with other components, may be mentioned.

The molded article of the present invention can be obtained by molding the polyester resin composition of the present invention. Specific examples of molded articles include electric and electronic parts such as covers for motors and the like, light bulb socket covers, automobile parts such as bumpers, injection coil covers, engine covers and wheel covers, and civil and housing-related building materials such as window sashes. , Hangers, chairs, trash cans and other household goods. Among them, it is suitable for molded articles requiring vibration-proof properties, impact resistance, and the like, and large molded articles.

[0028]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto.

The following polyethylene terephthalate was used as the component (A). A-1: Re-pellet product "recycled pet resin" of crushed bottle (made by Utsumi Planning Co., Ltd.)

As the component (B), the following ethylene-methyl acrylate copolymer was used. B-1: Ethylene-methyl acrylate copolymer "Aclift CG 4002" (manufactured by Sumitomo Chemical Co., Ltd., methyl acrylate content = 30% by weight)

The following epoxy group-containing ethylene copolymer was used as the component (C). C-1: Epoxy group-containing ethylene copolymer “Bond First 7L” (manufactured by Sumitomo Chemical Co., Ltd., glycidyl methacrylate content = 3% by weight, methyl acrylate content = 30% by weight, MFR (190 ° C., 2. 16kg) = 9
g / 10 minutes) C-2: an epoxy group-containing ethylene copolymer (manufactured by Sumitomo Chemical Co., Ltd., glycidyl methacrylate content = 1% by weight, methyl acrylate content) manufactured according to Japanese Patent Publication No. 48-11388. = 28% by weight, MFR (19
0 ° C., 2.16 kg) = 7 g / 10 min)

For comparison with the case containing the component (B), the following component (D) was used as an ethylene polymer in which the ethylenically unsaturated ester compound was not copolymerized. D-1: Polyethylene "Sumikasen G801" (Sumitomo Chemical Co., Ltd.)

(Examples 1 to 3 and Comparative Examples 1 to 5) The components (B) and (C) were blended with 100 parts by weight of the component (A) in accordance with the parts by weight shown in Table 1 to obtain a dry blend. After that, a coaxial twin-screw extruder having a diameter of 30 mm (L / D = 4
The mixture was melted and kneaded at a temperature of 290 ° C. at a screw rotation speed of 200 rpm and a supply speed of 18 kg / hour to obtain a pellet-shaped composition. Next, after drying the obtained composition at 120 ° C. for 6 hours using a dehumidifying dryer,
FR was measured. Subsequently, using an injection molding machine, molding temperature 2
90 ° C, 50 ° C mold temperature, Izod test specimen (thickness 3.175mm (1/8 inch), length 60.3-63.5mm, width 12.
7 ± 0.15mm (with V notch of 10.16 ± 0.05mm notch))
It was created. The obtained MFR and Izod impact strength are shown in Table 1.

<Evaluation Method> (1) Izod Impact Strength (KJ / m ² ) Evaluated according to ASTM D256. (2) MFR (g / 10 min) Evaluated according to JIS K7210 (290 ° C, 2.
16Kg).

[0035]

[Table 1] Polyester resin composition Izod compounding amount (parts by weight) Impact strength MFR S B-1 C-1 C-2 D-1 (KJ / m ² ) (g / 10 minutes) ―――――― ―――――――――――――――――――――――――――― Example 1 16.5 1.2 0 0 12.9 80 37.2 Example 2 7.0 4.0 0 0 5.3 72 81.5 Example 3 11.8 5.9 0 0 11.5 96 104.1 ―――――――――――――――――――――――――――――――――――― Comparative Example 10 0 17.6 0 5.6 33 126.8 Comparative Example 2 0 17.6 0 0 16.3 25 126.8 Comparative Example 3 1.1 4.2 0 0 1.8 87 64.4 Comparative Example 4 23.5 5.8 0 0 14.2 42 110.5 Comparative Example 5 0 5.9 0 11.8 4.7 79 78.5 ―――― ――――――――――――――――――――――――――――――――

[0036]

According to the present invention, a polyester resin composition having excellent fluidity and impact resistance can be obtained, and the flowability and impact resistance of polyester resin such as a pulverized PET bottle or a repellet thereof can be obtained. This gives a polyester resin composition having excellent heat resistance. The composition can be molded using a large-sized injection molding machine. Due to its excellent properties, for example, industrial raw materials, electric / electronic parts, automobile parts, civil engineering / house-related building materials, household goods, etc. Can be used as a molded article.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4F071 AA15 AA31 AA39 AA44 AA77 AA78 AH03 AH05 AH11 AH12 BA01 BB05 BB06 BC07 4J002 BB062 BB072 BB203 CD193 CF061 CF071 GL00 GQ00 GT00

Claims (10)

[Claims] 1. A composition comprising (A) a polyester resin, (B) a copolymer of ethylene and an ethylenically unsaturated ester compound, and (C) an epoxy group-containing ethylene copolymer,
A polyester resin composition in which the content (parts by weight) of the components (A) to (C) is 1 to 50 parts of the component (B) and 1 to 12 parts of the component (C) based on 100 parts of the component (A). In the following formula (1), S = 10.4 × ln [(B)] + 44.2 × ln [(C)] (1) (where [(B)] and [(C)] are respectively , (A)
It represents the content (parts by weight) of the components (B) and (C) based on 100 parts of the component. ) Is 20 to 110
And the total weight of the components (B) and (C) is (A)
6 parts or more of the polyester resin composition per 100 parts of the component. 2. The resin composition according to claim 1, wherein the component (A) is a polyethylene terephthalate resin containing polyethylene terephthalate as a main component. 3. The resin composition according to claim 1, wherein the component (A) is a crushed plastic bottle and / or a repellet plastic bottle. 4. The component (B) is based on 100% by weight of all monomer units constituting the component (B), and ethylene unit
The resin composition according to any one of claims 1 to 3, which is a copolymer containing 0 to 99% by weight and 1 to 50% by weight of an ethylenically unsaturated ester compound unit. 5. The resin composition according to claim 1, wherein the ethylenically unsaturated ester compound is a vinyl ester of a saturated carboxylic acid and / or an alkyl ester of an unsaturated carboxylic acid. 6. The component (C) is based on 100% by weight of all monomer units constituting the component (C), and ethylene units 2
0 to 99% by weight, epoxy group-containing monomer unit 1 to 30
The resin composition according to any one of claims 1 to 5, which is a copolymer containing 1% to 50% by weight of an ethylenically unsaturated ester unit. 7. The monomer of the epoxy group-containing monomer unit constituting the component (C) is represented by the following general formula (2): (Wherein, R represents an alkenyl group having 2 to 18 carbon atoms, and X represents a carbonyloxy group, a methyleneoxy group or a phenyleneoxy group). Resin composition. 8. A polyester resin composition having an MFR (melt flow rate) of 40 to 300 g / 10 min (290
2.16 kg).
8. The resin composition according to any one of the above items 7. 9. A method for improving the impact resistance and fluidity of a polyester resin, comprising using the resin composition according to claim 1. 10. A molded article comprising the resin composition according to claim 1.