JPH0665486A - Polyester resin composition - Google Patents

Abstract

PURPOSE:To provide a polyester resin composition containing a polyester and a graft copolymerization-reactional product of a specific copolymer and a modified polypropylene, containing the polyester and the polypropylene resin in highly compatibilized state and having excellent impact strength, rigidity, etc. CONSTITUTION:This resin composition is composed of (A) 1-50wt.% of a graft- copolymerization reactional product produced by melting and kneading (i) 5-95wt.% of a copolymer of ethylene, an unsaturated glycidyl compound (preferably glycidyl methacrylate) and an acrylate monomer (preferably methyl acrylate) with (ii) 95-5wt.% of a polypropylene modified with an unsaturated carboxylic acid (anhydride) and (B) 50-99wt.% of a polyester (preferably polybutylene terephthalate). The component A is produced preferably by kneading the components (i) and (ii) with a kneader such as twin-screw extruder in molten state at 230-280 deg.C. The unsaturated carboxylic acid (anhydride) is preferably a dicarboxylic acid (anhydride) such as maleic acid.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyester resin composition, and more particularly to a polyester resin composition in which a polyester and a polypropylene resin are well compatible with each other and which are excellent in impact resistance, rigidity and elongation properties.

[0002]

2. Description of the Related Art Polyester is used in various electrical components such as automobiles and home electric appliances due to its excellent insulating properties, mechanical strength and impact resistance. Especially when a large molded product is used, the weight becomes large. On the other hand, polypropylene is excellent in moldability, chemical resistance, water resistance and the like, but has a drawback that it is inferior in flexural modulus and impact resistance. Therefore, it has been attempted to blend such polyester and polypropylene to alleviate the drawbacks of both and make a well-balanced resin. However, since polypropylene and polyester are not sufficiently compatible with each other, there is a problem that impact resistance and surface peeling property are deteriorated simply by blending.

Therefore, in order to improve the compatibility, it has been attempted to compatibilize the polyester and the polypropylene by using a modified polyolefin with an unsaturated carboxylic acid or an anhydride thereof.

JP-A-60-58447 discloses a propylene polymer.
(A), thermoplastic polyester (B), modified propylene-α
-Olefin random copolymer (C), a composition comprising a styrene-butadiene block copolymer hydrogenated product (D) and an inorganic filler (E), a modified propylene-α-olefin random copolymer (C) Is a propylene-α-olefin random copolymer (F) having an X-ray crystallinity of 0 to 30% by weight and a propylene content of 50 to 70% by mole,
It is obtained by graft-modifying 0.01 to 5% by weight of a graft monomer selected from unsaturated carboxylic acids or their derivatives, and is based on 100 parts by weight of the total amount of the components (A) and (B).
Disclosed is a thermoplastic resin composition containing 1 to 80 parts by weight of component (C), 1 to 50 parts by weight of component (D) and 5 to 150 parts by weight of component (E).

However, in this polyester resin composition, the above components are usually kneaded at once, and the composition produced by such a method has a problem that the melt viscosity is low and the injection moldability is poor. Further, if an attempt is made to suppress the decrease in melt viscosity, there is a problem that compatibility elongation characteristics and the like are significantly decreased.

Therefore, it is an object of the present invention to provide a polyester resin composition in which polyester and polypropylene resin are well compatible with each other and which are excellent in impact resistance, rigidity and elongation properties.

[0007]

As a result of earnest studies in view of the above objects, the present inventors first found that a copolymer of ethylene, an unsaturated glycidyl compound and an acrylic acid-based monomer, and an unsaturated carboxylic acid or an anhydride thereof. To produce a graft copolymerization reaction product by melt-kneading modified polypropylene with a product,
The composition obtained by kneading this graft copolymerization reaction product, polyester, and, if necessary, further unmodified polypropylene has a good compatibilization of polyester and polypropylene resin, impact resistance, rigidity The present invention was conceived by finding that the resin has good elongation properties and the like.

That is, the first polyester resin composition of the present invention comprises (a) 5 to 95% by weight of a copolymer of ethylene, an unsaturated glycidyl compound and an acrylic acid-based monomer, and an unsaturated carboxylic acid or an anhydride thereof. 1 to 50% by weight of a graft copolymerization reaction product obtained by melt-kneading 95 to 5% by weight of modified polypropylene with a polyester, and (b) polyester 50 to 99
% By weight.

The second polyester resin composition of the present invention comprises (a) 5 to 95% by weight of a copolymer of ethylene, an unsaturated glycidyl compound and an acrylic acid-based monomer, and an unsaturated carboxylic acid or an anhydride thereof. Modified polypropylene by 95 ~
It is characterized by containing 1 to 45% by weight of a graft copolymerization reaction product obtained by melt-kneading 5% by weight, (b) 50 to 95% by weight of polyester, and (c) 49% by weight or less of polypropylene. And

The present invention will be described in detail below. [1] First Polyester Resin Composition First, the composition of the first polyester resin composition of the present invention is constituted.
Minutes will be explained. (a) Graft copolymerization reaction product In the present invention, the term (a) graft copolymerization reaction product means
Tylene, unsaturated glycidyl compounds and acrylic acid-based monomers
To the unsaturated carboxylic acid or its anhydride
Graft Copolymerization Reaction Product with Modified Polypropylene
Is.

Ethylene, unsaturated glycidyl compound and
Copolymer with acrylic acid-based monomer In this copolymer, the following are used as the (i) unsaturated glycidyl compound and (ii) acrylic acid-based monomer that are copolymerized with ethylene.

Examples of unsaturated glycidyl compounds include unsaturated glycidyl esters represented by the following general formula (1), unsaturated glycidyl ethers represented by the following general formula (2), and the like. .

[Chemical 1] (In the formula, R is 2 to 2 carbon atoms having an ethylenically unsaturated bond.
18 hydrocarbon groups. )

[Chemical 2] (In the formula, R is 2 to 2 carbon atoms having an ethylenically unsaturated bond.
18 is a hydrocarbon group of, X is -CH ₂ - is or a phenylene group. )

Specific examples of such unsaturated glycidyl esters include glycidyl acrylate, glycidyl methacrylate and glycidyl itaconic acid esters, and examples of unsaturated glycidyl ethers include allyl glycidyl ether and 2-methyl glycidyl ether. Examples thereof include allyl glycidyl ether and styrene-p-glycidyl ether. Glycidyl methacrylate is particularly preferable.

Examples of acrylic acid-based monomers include acrylic acid, methyl acrylate, ethyl acrylate, isopropyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate and the like. Of these, methyl acrylate is particularly preferable.

As a blending ratio of each component in the above copolymer, ethylene is preferably 50 to 94% by weight, particularly preferably 70 to 90% by weight, and the unsaturated glycidyl compound is 1 to
25% by weight, especially 2 to 15% by weight is preferred,
Acrylic acid monomer is 5-40% by weight, especially 15-35
It is preferably wt%.

The above-mentioned copolymer is a random copolymer in which an unsaturated glycidyl compound and an acrylic acid type monomer are introduced into the main chain of ethylene, or an unsaturated glycidyl compound and acrylic acid as a side chain of an ethylene polymer. Any graft copolymer into which a system monomer is introduced may be used.

In the case of a random copolymer, ethylene, an unsaturated epoxy compound and an acrylic acid type monomer may be radically polymerized at atmospheric pressure.

The graft copolymer can be produced by either a solution method or a melt-kneading method. In the melt-kneading method, polyethylene, an unsaturated glycidyl compound, an acrylic acid-based monomer, and a catalyst are charged into an extruder, a twin-screw kneader, or the like, and heated to a temperature of 150 to 300 ° C to knead while melting. When the solution method is used, the above starting materials are dissolved in an organic solvent such as xylene and the temperature is adjusted to 80 to 140 ° C.
With stirring at the temperature. In any case, it is possible to use a normal radical polymerization catalyst as a catalyst, for example, benzoyl peroxide, lauroyl peroxide, ditertiary butyl peroxide, acetyl peroxide, tert-butyl peroxybenzoic acid, dicumyl peroxide, Peroxybenzoic acid, peroxyacetic acid, tertiary butyl peroxypivalate, peroxides such as 2,5-dimethyl-2,5-ditertiary butyl peroxyhexyne, and diazo compounds such as azobisisobutyronitrile Etc. are preferred.

The weight average molecular weight of such a copolymer is 1
The melt flow rate (MFR, 230 ℃, 2.16kg load) is 0.5 to 50 g / 10
Minutes.

Modified polypropylene Modified polypropylene is polypropylene modified with unsaturated carboxylic acid or its anhydride. Polypropylene is a crystalline polymer obtained by polymerizing a propylene monomer as a main component, and is not limited to a homopolymer, but includes a block copolymer or a random copolymer of propylene and another α-olefin such as ethylene. In the case of copolymers, propylene-ethylene random copolymers are preferred. In this case, the ethylene content is preferably 1 to 10% by weight. Such polypropylene is usually 0.01-100 g /
10-minute melt flow rate (MFR, JISK7210, load 2.16)
kg, 230 ° C).

Further, propylene and the general formula (3)

[Chemical 3] (However, R ₁ to R ₄ are H or an alkyl group having 1 to 6 carbon atoms, and n is an integer of 1 to 20) and a non-conjugated diene comonomer. A random copolymer (hereinafter referred to as PPDM) or the like may be used.

Examples of the non-conjugated diene include 2-methyl-1,4-pentadiene, 1,4-hexadiene, 4-methylidene-1-hexene, 4-methyl-1,4-hexadiene, 5-methyl- 1,4-hexadiene, 1,4-heptadiene, 4-ethyl
-1,4-hexadiene, 4,5-dimethyl-1,4-hexadiene, 4-methyl-1,4-heptadiene, 4-ethyl-1,4-heptadiene, 5-methyl-1,4-heptadiene, 5 -Methyl-1,4
-Octadiene, 1,5-heptadiene, 1,5-octadiene, 5-methyl-1,5-heptadiene, 6-methyl-1,5-heptadiene, 2-methyl-1,5-hexadiene, 1,6-octadiene , 6-methyl-1,6-octadiene, 7-methyl-1,6-octadiene, 2-methyl-1,6-heptadiene, 1,9-decadiene, 1,13-tetradecadiene and the like. Of these, 1,4-hexadiene, 2-methyl-1,5-hexadiene, 7-methyl-1,6-octadiene, 1,9-decadiene and 1,13-tetradecadiene are particularly preferable. Two or more kinds of these non-conjugated diene comonomers may be mixed and used.

In order to randomly copolymerize propylene and a non-conjugated diene comonomer, a general copolymerization method using a Ziegler-Natta catalyst may be applied. In this case, it is desirable that the proportion of the non-conjugated diene is 0.05 to 10 mol%. When the content of the non-conjugated diene is less than 0.05 mol%, a high graft ratio cannot be obtained in the graft reaction of the unsaturated carboxylic acid or its anhydride described later. Further, if it exceeds 10 mol%, the crystallinity of the copolymer is significantly lowered. The content of the non-conjugated diene is more preferably 0.1 to 3 mol%.

The random copolymer includes ethylene,
Other unsaturated monomers such as butene-1 may be copolymerized at 5 mol% or less.

As described above, the term "polypropylene" used in the present specification is not limited to a homopolymer of propylene, and should be understood to include each copolymer as described above.

Examples of unsaturated carboxylic acids or their anhydrides which modify polypropylene include monocarboxylic acids such as acrylic acid and methacrylic acid, dicarboxylic acids such as maleic acid, fumaric acid and itaconic acid, and maleic anhydride. Itaconic anhydride, endo-bicyclo- [2,2,1] -5
Examples thereof include dicarboxylic acid anhydrides such as -heptene-2,3-dicarboxylic acid anhydride (hymic anhydride), and dicarboxylic acid and its anhydride are particularly preferable.

The polypropylene modified with the unsaturated carboxylic acid or its anhydride may be a block copolymer, a graft copolymer, a random copolymer or an alternating copolymer.

The content of unsaturated carboxylic acid or its anhydride in the modified polypropylene is 0.01 to 10% by weight, preferably
0.2 to 10% by weight. When the amount of modification with an unsaturated carboxylic acid or its anhydride is less than 0.01% by weight, there is no sufficient effect to improve the compatibility between the polypropylene resin and the polyester resin, and when it exceeds 10% by weight, the mechanical strength is descend. Specifically, when modifying with maleic anhydride and hymic acid anhydride, the content of each is 0.2
-5% by weight, particularly 0.3-3% by weight is preferred.

The melt flow rate of the modified polypropylene as described above is in the range of 0.1 to 400 g / 10 min.

The modified polypropylene can be produced by either a solution method or a melt kneading method. In the case of the melt kneading method, polypropylene, modifying unsaturated carboxylic acid (or acid anhydride) and a catalyst are charged into an extruder or a twin-screw kneader,
Knead while heating to a temperature of 180-300 ℃.
In the case of the solution method, the above-mentioned starting materials are dissolved in an organic solvent such as xylene and the stirring is carried out at a temperature of 90 to 150 ° C. In either case, the same catalyst as the above radical polymerization catalyst can be used. The amount of catalyst added is 1 to 100 parts by weight of the unsaturated carboxylic acid for modification or its anhydride.
It is about 100 parts by weight.

The graft copolymerization reaction product of the copolymer of (1) and modified polypropylene can be obtained by mixing them and dynamically heat-treating them. in this case,
The mixture is kneaded in a heated and molten state at 220 to 300 ° C, preferably 230 to 280 ° C, using a kneading machine such as a single-screw extruder, a twin-screw extruder, a Banbury mixer, a kneading roll, and a Brabender. If the kneading temperature is lower than 220 ° C, a sufficient graft copolymerization reaction product cannot be obtained, while if it exceeds 300 ° C, decomposition of the resin component is likely to occur.

The blending ratio of the copolymer of (1) and the modified polypropylene is 5 to 95% by weight, preferably 2% by weight of the copolymer.
0 to 80% by weight, modified polypropylene 95 to 5% by weight, preferably 80 to 20% by weight.

However, the entire graft copolymerization reaction product is
It is preferable that the content of the unsaturated carboxylic acid or its anhydride is 0.05% by weight or more, and the content of the acrylic acid-based monomer is 1% by weight or more, as 100% by weight. When the content of unsaturated carboxylic acid or its anhydride is less than 0.05% by weight and / or the content of acrylic acid type monomer is less than 1% by weight, the obtained graft copolymerization reaction product is a phase of polypropylene resin and polyester. It becomes difficult to exert a sufficient effect for improving the solubility.

The melt flow rate (MFR, 230 ° C., 2.16 kg load) of the above graft copolymerization reaction product is preferably in the range of 0.05 to 20 g / 10 minutes.

(B) Polyester In the present invention, the polyester is a thermoplastic resin generally composed of saturated dicarboxylic acid and saturated dihydric alcohol, such as polyethylene terephthalate, polypropylene terephthalate, polytetramethylene terephthalate (polybutylene terephthalate), polyhexamethylene. Examples thereof include terephthalate, polycyclohexane-1,4-dimethylol terephthalate and polyneopentyl terephthalate. Of these, polyethylene terephthalate and polybutylene terephthalate are particularly preferable, and polybutylene terephthalate is particularly preferable.

The above polyester preferably has an intrinsic viscosity [η] of 0.30 to 1.8 and a concentration of terminal carboxyl groups of 10 to 200 meq / kg. Here, the intrinsic viscosity [η] (dl
/ g) is determined from the solution viscosity measured at 25 ° C. in an o-chlorophenol solvent.

In the case of polybutylene terephthalate, the intrinsic viscosity [η] is 0.30 to 1.8 and the terminal carboxyl group concentration is
It is preferably 10 to 200 meq / kg. Also in this case, the terephthalic acid component may be substituted with an alkyl group, a halogen group or the like, and the glycol component may be 1,4-butylene glycol or other glycol such as ethylene glycol up to about 50% by weight. It may contain propylene glycol, hexamethylene glycol or the like.

In the case of polyethylene terephthalate, the intrinsic viscosity [η] is preferably 0.30 to 1.2 and the terminal carboxyl group concentration is preferably 10 to 200 meq / kg. The terephthalic acid component in polyethylene terephthalate may be substituted with an alkyl group, a halogen group or the like, and the glycol component may be other than ethylene glycol.
Other glycols such as 1,4-butylene glycol, propylene glycol and hexamethylene glycol may be contained up to about 50% by weight.

The mixing ratio of the components (a) and (b) as described above is such that (a) the graft copolymerization reaction product is 1 to 50% by weight, preferably 15 to 40% by weight, and (b) The polyester is 50 to 99% by weight, preferably 60 to 85% by weight.

(A) 1% by weight of the graft copolymerization reaction product
Below (when (b) polyester exceeds 99% by weight),
If the elongation characteristics and the like are not sufficient and (a) the graft copolymerization reaction product exceeds 50% by weight ((b) the polyester content is less than 50% by weight), the rigidity decreases.

The first polyester resin composition of the present invention has the above composition, but for the purpose of further strengthening and modifying it, other fillers and reinforcing materials, heat stabilizers, light stabilizers,
A flame retardant, a plasticizer, an antistatic agent, a foaming agent, a nucleating agent, etc. can be added.

[2] Second Polyester Resin Composition Next, the constituent components of the second polyester resin composition of the present invention will be described. The second polyester resin composition of the present invention is basically the above first polyester resin composition to which (c) unmodified polypropylene is added.
Therefore, as the (a) graft copolymerization reaction product and the (b) polyester, the same ones as described above can be used.

(C) Polypropylene As the polypropylene in the present invention, the same polypropylene as the above-mentioned modified polypropylene can be used, but propylene homopolymer and propylene-ethylene block copolymer are particularly preferable. Such polypropylenes usually have a melt flow rate (MFR, JISK7210, load 2.16kg, 230
℃).

Further, the polypropylene is ethylene,
Olefin such as propylene, 1-butene, 1-hexene, copolymer rubber of two or more kinds of α-olefins such as 4-methyl-pentene, or copolymer rubber of α-olefin and other monomer 20% by weight of thermoplastic elastomer
It may be contained to some extent.

The copolymer rubber of two or more of the above α-olefins is typically ethylene-propylene copolymer rubber (EPR), ethylene-butene copolymer rubber (EBR) and Examples thereof include ethylene-propylene-diene copolymer rubber (EPDM).

The mixing ratio of each component as described above is (a)
The total amount of + (b) + (c) is 100% by weight, and (a) the graft copolymerization reaction product is 1 to 45% by weight, preferably 15 to
40% by weight, (b) polyester is 50 to 95% by weight, preferably 60 to 85% by weight, and (c) polypropylene is 49% by weight or less, preferably 25% by weight or less.

(A) 1% by weight of the graft copolymerization reaction product
When it is less than 50% by weight, the elongation properties and the like are not sufficient, while when it exceeds 50% by weight, moldability and rigidity are deteriorated. (b) When the polyester content is less than 50% by weight, moldability and rigidity are deteriorated, while
If it exceeds 95% by weight, the elongation properties will be insufficient. Further, if the content of (c) polypropylene exceeds 49% by weight, elongation and rigidity will decrease.

It should be noted that (a) the graft copolymerization reaction product and (c)
Polypropylene is the sum of both resin components
It is preferably from 15 to 40% by weight with respect to 100% by weight. In addition, the total amount of (a) graft copolymerization reaction product plus (a) graft copolymerization reaction product + (c) polypropylene is 100
The weight% is preferably 20% by weight or more. When the graft copolymerization reaction product is less than 20% by weight, there is no sufficient effect for improving the compatibility between polypropylene and polyester and improving the elongation property of the resulting composition. The particularly preferable content of the graft copolymerization reaction product is about 30% by weight or more.

The same various additives as described above can be added to the second polyester resin composition of the present invention.

[3] Production Method The first and second polyester resin compositions of the present invention as described above are both the above polyester and graft copolymerization reaction product (in the case of the second composition, polypropylene is further used). Is added by a kneading machine such as a single-screw extruder, a twin-screw extruder, a Banbury mixer, a kneading roll, and a Brabender at 220 to 300 ° C, preferably 230 to 280 ° C in a molten state. be able to. The melt-kneading may be carried out in a batch or in two or more steps for each component.

[0051]

The first and second polyester resin compositions of the present invention melt a copolymer of ethylene, an unsaturated glycidyl compound and an acrylic acid-based monomer, and a modified polypropylene with an unsaturated carboxylic acid or an anhydride thereof. Graft copolymerization reaction product obtained by kneading, polyester, and, if necessary, further contains unmodified polypropylene, so that the polyester and polypropylene resin are well compatibilized, impact resistance, Good rigidity and elongation characteristics.

Although the reason why such an effect is obtained is not necessarily clear, it is because the graft copolymer of the above copolymer and the modified polypropylene is very well compatible with the polyester by using the above copolymer. It is believed that there is.

[0053]

The present invention will be described in more detail with reference to the following specific examples. In each of the examples and comparative examples, the following materials were used as raw materials and additives. [1] Polyester-polybutylene terephthalate PBT: [TRB H manufactured by Teijin Ltd., intrinsic viscosity [η] 1.07] [2] Polypropylene homopolypropylene HPP: [Y-201 manufactured by Tonen Kagaku KK, melt flow rate ( MFR, 230 ℃, 2.16kg load) 1.5 g / 10 minutes] [3] Copolymer of ethylene, unsaturated glycidyl compound and acrylic acid monomer Ethylene-glycidyl methacrylate-methyl acrylate copolymer-E-GMA- MA-1: [Bonto First 7L, Sumitomo Chemical Co., Ltd., glycidyl methacrylate content 3% by weight, methyl acrylate content 30% by weight, MFR 9] ethylene-glycidyl methacrylate-methyl acrylate copolymer-E- GMA-MA-2: [Sumitomo Chemical Co., Ltd., Bontofast 7M, glycidyl methacrylate content 6% by weight, methyl acrylate content 30% by weight, MFR 9] [4] Styrene and a copolymer of ethylene with an unsaturated glycidyl compound - glycidyl methacrylate copolymer · E-GMA: [Sumitomo Chemical Co., Ltd. Bonto Fast
E, glycidyl methacrylate content 12% by weight)

Synthesis Example 1 Synthesis of modified polypropylene 100 parts by weight of homopolypropylene (HPP), 1 part by weight of maleic anhydride (MAH), and 0.2 parts by weight of a radical generator (POX, Perhexin 25B, manufactured by NOF Corporation). Mix with
Using a twin-screw extruder with an L / D of 30 and a diameter of 45 mm,
The mixture was kneaded at 200 ° C under a condition of ° C and a graft reaction was carried out to obtain a modified polypropylene (CMPP).

The melt flow rate (230 ° C., 2.16 kg load) of the obtained modified polypropylene was 100 g / 10 minutes. The graft ratio of maleic anhydride is 0.3% by weight.
Met.

Synthesis Example 2 Synthesis of Graft Copolymerization Reaction Product 10 parts by weight of ethylene-glycidyl methacrylate-methyl acrylate copolymer (E-GMA-MA-1) and 10 parts by weight of modified polypropylene (CMPP) After dry blending with a Henschel mixer, a twin-screw extruder having a screw diameter of 45 mm and L / D = 28 was kneaded at 250 ° C. and 200 rpm to obtain a graft copolymerization reaction product (GR).

Synthesis Example 3 Synthesis of Graft Copolymerization Reaction Product 16 parts by weight of ethylene-glycidyl methacrylate-methyl acrylate copolymer (E-GMA-MA-1) and 4 parts by weight of modified polypropylene (CMPP) After dry blending with a Henschel mixer, a twin-screw extruder having a screw diameter of 45 mm and L / D = 28 was kneaded at 250 ° C. and 200 rpm to obtain a graft copolymerization reaction product (GR).

Synthesis Example 4 Synthesis of Graft Copolymerization Reaction Product 10 parts by weight of ethylene-glycidyl methacrylate-methyl acrylate copolymer (E-GMA-MA-2) and 10 parts by weight of modified polypropylene (CMPP) were prepared. After dry blending with a Henschel mixer, a twin-screw extruder having a screw diameter of 45 mm and L / D = 28 was kneaded at 250 ° C. and 200 rpm to obtain a graft copolymerization reaction product (GR).

Synthesis Example 5 Synthesis of Graft Copolymerization Reaction Product Ethylene-glycidyl methacrylate copolymer (E-GMA)
After dry blending 10 parts by weight and modified polypropylene (CMPP) 10 parts by weight with a Henschel mixer, a twin screw extruder with screw diameter 45 mmφ and L / D = 28
Kneaded at 0 ° C and 200 rpm to obtain graft copolymerization reaction product
(GR) was obtained.

Examples 1 to 5 and Comparative Examples 1 and 4 Polyester (PBT) and graft copolymerization reaction product (G
R to GR) in a ratio shown in Table 1, and after dry blending with a Henschel mixer, the screw diameter is 45 mm.
A twin screw extruder of φ, L / D = 28 was kneaded at 250 ° C. and 200 rpm to obtain a polyester resin composition.

The melt flow rate (250 ° C., 2.16 kg load) of the polyester resin composition thus obtained,
Tensile yield strength, tensile elongation at break, flexural modulus, Izod impact strength, specific gravity and compatibility were measured. The results are shown in Table 2.

Comparative Example 2 and Comparative Example 5 Polyester (PBT) and ethylene-glycidyl methacrylate-methyl acrylate copolymer (E-GMA-MA-1) were dried by a Henschel mixer at the ratio shown in Table 1. After blending, a twin screw extruder having a screw diameter of 45 mm and L / D = 28 was kneaded at 250 ° C. and 200 rpm to obtain a polyester resin composition.

The melt flow rate (250 ° C., 2.16 kg load) of the polyester resin composition thus obtained,
Tensile yield strength, tensile elongation at break, flexural modulus, Izod impact strength, specific gravity and compatibility were measured. The results are shown in Table 2.

Comparative Examples 3 and 6 Polyester (PBT) and modified polypropylene (CMP
P) with the ratio shown in Table 1, after dry blending with a Henschel mixer, screw diameter 45 mmφ, L / D =
Kneading was carried out at 250 ° C. and 200 rpm with a 28-screw extruder to obtain a polyester resin composition.

The melt flow rate (250 ° C., 2.16 kg load) of the polyester resin composition thus obtained,
Tensile yield strength, tensile elongation at break, flexural modulus, Izod impact strength, specific gravity and compatibility were measured. The results are shown in Table 2.

Table 1 Composition weight part Example 1 Example 2 Example 3 Example 4 Example 5 PBT 80 80 80 80 60 90 GR 20 − − 40 10 GR − − 20 − − GR − 20 − − −

Table 1 (continued) Composition Weight Part Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 PBT 80 80 80 80 60 60 60 GR 20 − − 40 − − E-GMA- MA-1-20--40-CMPP--20--40

Table 2 Physical Properties Example 1 Example 2 Example 3 Example 4 Example 5 MFR ⁽¹⁾ 6 7 5 2 12 Tensile yield strength ⁽²⁾ 410 420 400 350 440 Tensile elongation at break ⁽³⁾ 240 150 260 220 220 Flexural modulus ⁽⁴⁾ 17000 18000 16000 13000 20000 Izod impact strength ⁽⁵⁾ 23 ℃ 25 22 35 NB ^* 16 −30 ℃ 9 8 12 18 6 Specific gravity ⁽⁶⁾ 1.21 1.21 1.21 1.13 1.26 Compatibility ^{( 7)} ○ ○ ○ ○ ○

Table 2 (continued) Physical Properties Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 MFR ⁽¹⁾ 2 4 20 0.5 0.2 15 Tensile Yield Strength ⁽²⁾ 420 400 480 360 320 380 Tensile elongation at break ⁽³⁾ 200 220 10 200 150 20 Flexural modulus ⁽⁴⁾ 18000 13000 20000 14000 12000 15000 Izod impact strength ⁽⁵⁾ 23 ℃ 14 20 4 35 25 7 -30 ℃ 4 6 3 12 10 3 Specific gravity ⁽⁶⁾ 1.21 1.22 1.20 1.13 1.13 1.12 Compatibility ⁽⁷⁾ ○ ○ × ○ ○ ×

(1) MFR: 250 ° C. according to ASTM D1238, 2.
Measured with a load of 16 kg (unit: g / 10 minutes). (2) Tensile yield strength: Measured according to ASTM D638 (Unit: kg /
cm ² ). (3) Tensile elongation at break: measured by ASTM D638 (unit:%)
. (4) Flexural modulus: measured by ASTM D790 (Unit: kg / cm
² ). (5) Izod impact strength: Measured with ASTM D256 at 23 ° C with a notch (unit: kg · cm / cm). (6) Specific gravity: Measured according to ASTM D792. (7) Compatibility: 1mm x 1mm using a razor on the surface of the test piece
100 squares were attached, cellophane tape (manufactured by Nichiban Co., Ltd.) was attached to the squares, and then stripped. Of the 100 squares, count the number of squares that did not adhere to the cellophane tape and remained on the surface of the test piece.
Evaluated as.

Examples 6 to 10 and Comparative Examples 7 to 10 Polyester (PBT), polypropylene (HPP), and graft copolymerization reaction products (GR to GR) were mixed in a ratio shown in Table 3 by a Henschel mixer. After dry blending, a twin screw extruder having a screw diameter of 45 mmφ and L / D = 28 was kneaded at 250 ° C. and 200 rpm to obtain a polyester resin composition.

The melt flow rate (250 ° C., 2.16 kg load) of the polyester resin composition thus obtained,
Tensile yield strength, tensile elongation at break, flexural modulus, Izod impact strength, specific gravity and compatibility were measured. The results are shown in Table 4.

Table 3 Composition parts by weight Example 6 Example 7 Example 8 Example 9 Example 10 PBT 60 60 60 60 60 80 HPP 20 20 20 20 30 15 15 GR 20 − − 10 5 GR − 20 − − − GR − − 20 − −

[0074]

4th Table Physical Properties Example 6 Example 7 Example 8 Example 9 Example 10 MFR 9 4 12 15 17 Tensile Yield Strength 370 360 380 400 450 Tensile Rupture Elongation 140 220 110 100 120 Flexural Modulus 14000 13000 15000 16000 19000 Izod impact strength 23 ℃ 14 36 12 10 8 -30 ℃ 6 12 4 4 4 Specific gravity 1.12 1.13 1.13 1.12 1.20 Compatibility ○ ○ ○ ○ ○

Table 4 (continued) Physical Properties Comparative Example 7 Comparative Example 8 Comparative Example 9 Comparative Example 10 MFR 8 10 12 15 Tensile Yield Strength 380 390 430 410 Tensile Rupture Elongation 180 60 80 5 Flexural Modulus 15000 16000 18000 17000 Izod impact strength 23 ℃ 7 5 6 2 -30 ℃ 4 3 4 2 Specific gravity 1.12 1.12 1.20 1.20 Compatibility ○ ○ ○ ×

As is clear from Tables 2 and 4, the first and second polyester resin compositions of the present invention have tensile yield strength, tensile elongation at break, flexural modulus, Izod impact strength, specific gravity and All of the compatibility was good. On the other hand, the polyester resin composition of each comparative example was significantly inferior in any one of the above physical properties.

[0078]

As described in detail above, the polyester resin composition of the present invention is a polypropylene modified with a copolymer of ethylene, an unsaturated glycidyl compound and an acrylic acid monomer, and an unsaturated carboxylic acid or an anhydride thereof. Since the graft copolymerization reaction product obtained by melt-kneading and, polyester, and optionally unmodified polypropylene are further contained, the polyester and the polypropylene resin are well compatibilized, Good impact resistance, rigidity and elongation characteristics.

The polyester resin composition of the present invention as described above is used as various engineering plastics, in particular, automobile interior and exterior parts, home electric appliance parts, industrial material parts,
It is suitable as a resin composition for injection molded products such as packaging materials.

Claims (2)

[Claims] 1. (a) A copolymer of ethylene, an unsaturated glycidyl compound and an acrylic acid-based monomer in an amount of 5 to 95% by weight,
1 to 50% by weight of a graft copolymerization reaction product obtained by melt-kneading 95 to 5% by weight of modified polypropylene with an unsaturated carboxylic acid or an anhydride thereof, and (b) polyester 50 to 50% by weight.
99% by weight of the polyester resin composition. 2. (a) 5 to 95% by weight of a copolymer of ethylene, an unsaturated glycidyl compound and an acrylic acid-based monomer,
1 to 45% by weight of a graft copolymerization reaction product obtained by melt-kneading 95 to 5% by weight of a modified polypropylene with an unsaturated carboxylic acid or an anhydride thereof, and (b) a polyester 50
A polyester resin composition characterized by containing ˜95% by weight and (c) polypropylene 49% by weight or less.