JPS61221260A - Thermoplastic polyester composition - Google Patents

Abstract

PURPOSE:To provide a resin compsn. having excellent low-temperature impact resistance and improved melt flow characteristics, by blending an unsaturated carboxylic acid/alpha-olefin copolymer and an unsaturated epoxy compd./alpha-olefin copolymer with a thermoplastic polyester. CONSTITUTION:A compsn. consists of 50-98pts.wt. thermoplastic polyester (A), 1-49pts.wt. unsaturated carboxylic acid or anhydride/alpha-olefin copolymer (B) having an unsaturated carboxylic acid or anhydride (D) content of 0.05-30wt% and 1-49pts.wt. unsaturated epoxy compd./alpha-olefin copolymer (C) having an unsaturated epoxy compd. (E) content of 0.05-30wt%. At least one of said copolymers B and C is a copolymer obtd. by grafting an unsaturated carboxylic acid or anhydride (D) or an unsaturated epoxy compd. (E) onto an ethylene/alpha-olefin copolymer (F) having an ethylene content of 70-95mol% and a crystallinity by X-rays of 30% or below.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a thermoplastic polyester composition that has excellent impact resistance, particularly impact resistance at low temperatures, and improved melt flowability.

[Conventional technology]

Thermoplastic polyesters such as polyethylene terephthalate are widely used as packaging materials for films, sheets, containers, etc. due to their excellent properties such as mechanical strength, rigidity, heat resistance, chemical resistance, and oil resistance. In recent years, these properties have been utilized as so-called engineering plastics to be applied to some mechanical parts, electrical appliance parts, and automobile parts. However, although thermoplastic polyesters such as polyethylene terephthalate have the above-mentioned properties, they have inferior impact resistance compared to polycarbonate, etc., so they are currently not widely used in fields that require high impact resistance. .

Methods for improving the impact resistance of thermoplastic polyester include 1, for example, a method of adding and mixing ethylene propylene rubber-polyisobutene or polybutene to polyester (Japanese Patent Publication No. 46-5225); A method of melt-mixing modified ethylene polymers with a crystallinity of 755c or less obtained by graft polymerization of unsaturated carboxylic acids or derivatives thereof (Japanese Patent Publication No. 57-5405
8, Japanese Patent Publication No. 57-59261), or derivatives of thermoplastic polyester and α,β-unsaturated carboxylic acid.

Compositions with specific random copolymers having polar groups such as unsaturated epoxides (Japanese Patent Publication No. 59-28223, etc.) have been proposed. However, in the former method, the impact resistance is not sufficiently improved due to the poor compatibility between polyester and ethylene/propylene rubber, and in the latter two methods, although the impact strength is considerably improved, it depends on the application. was still insufficient.

Furthermore, α-olefin and α are added to polyester.

A composition prepared by adding and mixing a copolymer with glycidyl ester of β-unsaturated acid and an ethylene copolymer (JP-A-58
-17148) or polyester grafted with an unsaturated carboxylic acid or its anhydride.
- It has been disclosed that a composition (JP-A-60-28446) in which an olefin copolymer and a polyepoxy compound are added and mixed has high impact resistance at low temperatures. However, although all of these compositions have considerably improved impact resistance at low temperatures, they are still insufficient depending on the application, and all such compositions have reduced melt flowability and may have difficulty in moldability. Do you get it.

[Problem that the invention seeks to solve]

In view of this situation, the present inventors investigated to obtain a thermoplastic polyester composition that has further excellent impact resistance at low temperatures and improved melt flowability. Or its anhydride α
- A composition obtained by adding and melt-mixing an olefin copolymer and a specific unsaturated epoxide compound/α-olefin copolymer has the above-mentioned properties, and also has excellent rigidity and heat resistance. As a result, we have completed the present invention.

[Means for solving problems]

That is, 1 the present invention is (a) thermoplastic polyester (A) 50 to 98
Weight part.

(b) Unsaturated carboxylic acid or its anhydride (D)
Unsaturated carboxylic acid or its anhydride/α-olefin copolymer (B) 1 with a content of 0.05 to 30% by weight
and (c) an unsaturated epoxide compound (E) content of 0.0 to 49 parts by weight.
05 to 30% by weight of unsaturated epoxide compound α-
1 to 49 parts by weight of olefin copolymer (C).

and at least one of the α-olefin copolymer IB) or (C) has an ethylene content of 70 to 95 mol% and an X-ray crystallinity of 30.
% or less of an ethylene/α-olefin copolymer (F) and an unsaturated carboxylic acid or its anhydride [D) or an unsaturated epoxide compound IE). The object of the present invention is to provide a thermoplastic polyester composition that has heat resistance, excellent impact resistance, and melt flowability.

[For production]

The thermoplastic polyester CA) used in the present invention is an aliphatic glycol such as ethylene glycol, propylene glycol, 1,4-phthanediol, neopentyl glycol, hexamethylene glycol, etc.

An alicyclic glycol such as cyclohexane dimetatool, an aromatic dihydroxy compound such as bisphenol, or a dihydroxy compound unit selected from two or more of these, and terephthalic acid, isophthalic acid, 2,6-naphthalene dicarboxylic acid, etc. aromatic dicarboxylic acid, oxalic acid,
Succinic acid, adipic acid.

A polyester formed from aliphatic dicarboxylic acids such as sebacic acid and undecadicarboxylic acid, alicyclic dicarboxylic acids such as hexahydroterephthalic acid, or dicarboxylic acid units selected from two or more of these, As long as it exhibits plasticity, it may be modified with a small amount of triol or tricarboxylic acid or higher polyhydroxy compound such as tricarboxylic acid, polycarboxylic acid, or the like. Specific examples of these thermoplastic polyesters include polyethylene terephthalate, polybutylene terephthalate, and polyethylene isophthalate/terebutalate copolymers. Among them, polybutylene terephthalate.

Polyethylene terephthalate is preferred because it has excellent mechanical properties and moldability.

Unsaturated carboxylic acid or its anhydride used in the present invention
The α-olefin copolymer (B) (hereinafter abbreviated as carboxylic acid copolymer IB) has an unsaturated carboxylic acid or its anhydride+D) content of 0.05 to 30% by weight.

Preferably 0.1 to 20% by weight of the a-olefin copolymer (normal melt flow rate) (MFR: A
STM D 12!18. If the α-olefin is mainly ethylene, condition E, otherwise condition L) is 0o01 to 5.
0g/10m1n, preferably 0.05 to 30jC
/10m1n.

In the carboxylic acid copolymer (B), the content of unsaturated carboxylic acid or its anhydride is 0.05% by weight.
If it is less than that, the dispersibility and affinity for the thermoplastic polyester (thermoplastic polyester) will be poor, and the impact resistance will not be improved, nor will the melt flowability be improved. On the other hand, if it exceeds 50% by weight, the copolymer (B) itself loses its flexibility, so that the dispersibility of the thermoplastic polyester powder cannot be improved.

The unsaturated carboxylic acid or its anhydride (D) in the carboxylic acid copolymer (B) is acrylic acid.

Maleic acid, fumaric acid, tetrahydrophthalic acid.

itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, nadic acid (endocys-bicyclo(2,2,1
) hept-5-ene-2,5-dicarboxylic acid), or anhydrides thereof. Among these, unsaturated dicarboxylic acids or their anhydrides are preferred, and maleic acid, nadic acid (2), and their anhydrides are particularly preferred.

In addition, α-olefins are usually α-olefins having 2 to 20 carbon atoms.
An olefin, specifically ethylene.

Propylene, 1-butene, 1-hexene, 4-methyl-
Examples include 1-pentene, 1-octene, 1-decene, and the like. These α-olefins may be used alone or in combination of two or more.

The carboxylic acid copolymer (B) in the present invention is a random copolymer or a block copolymer obtained by copolymerizing an unsaturated carboxylic acid or its anhydride during the polymerization of an α-olefin, or a pre-polymerized It contains a graft polymer obtained by graft-polymerizing an unsaturated carboxylic acid or its anhydride (TD) onto a poly-α-olefin.

The unsaturated epoxide compound/α-olefin copolymer (C) (hereinafter abbreviated as epoxy copolymer (C)) used in the present invention has an unsaturated epoxide compound (E) content of 0.0.
5 to 30% by weight, preferably 0.1 to 20% by weight of a copolymer with α-olefin (1 usually melt flow rate) (MFR: ASTM D 1238° Condition E% if the α-olefin is mainly ethylene) Other conditions are L)
is in the range of 0.01 to 50 g/l 0 m1n, preferably 0.05 to 50 g/710 min.

In the above-mentioned epoxy copolymer tc), if the content of the unsaturated epoxide compound (K) is less than 0.01% by weight, the dispersibility and affinity for thermoplastic polyester particles are poor, so impact resistance is not improved. On the other hand, if it exceeds 30% by weight, the copolymer IB) itself loses its flexibility, so even if it is added to the thermoplastic polyester (4), the impact resistance will not be improved.

The unsaturated epoxide compound (IC) in the epoxy copolymer (C) can be copolymerized with the α-olefin.
It is a compound that has an unsaturated bond consisting of an olefinic double bond and an epoxy group in the molecule, and specifically includes glycidyl methacrylate, glycidyl acrylate, allyl glycidyl ether, vinyl dalicidyl ether, and glycidyl itaconate.

Aliphatic glycidyl ester or aliphatic glycidyl ether such as glycidyl maleate, 2-cyclohexene-1-glycidyl ether, cyclohexene-4,5-
Dicarboxylic diglycidyl ester, cyclohexene
4-carboxylic acid glycidyl ester, 5-norbornene-2-methyl-2-carboxylic acid glycidyl ester, endocis-bicyclo[2°2.1)-5-hebutene-
Examples include alicyclic glycidyl esters and alicyclic glycidyl ethers such as 2,3-dicarboxylic acid diglycidyl ester.

In addition, α-olefins are usually α-olefins having 2 to 20 carbon atoms.
An olefin, specifically ethylene.

Propylene, 1-butene, 1-hexene, 4-methyl-
Examples include 1-pentene, 1-octene, 1-decene, and the like. These α-olefins may be used alone or in combination of two or more.

The epoxy copolymer (C) in the present invention is a random copolymer or block copolymer obtained by copolymerizing an unsaturated epoxide compound (E) during the polymerization of an α-olefin, and a prepolymerized polyα-olefin. It contains a graft polymer obtained by graft polymerizing an unsaturated epoxide compound (E).

At least one of the carboxylic acid copolymer (B) or the epoxy copolymer (C) used in the present invention has an ethylene content of 70 to 95 mol%, preferably 75 to 92 mol%, and a crystallinity of 30% by xm. The following is preferred 25
1% or less of low crystallinity or non-quality ethylene/α-olefin copolymer (F), usually MFR [E) (AS
TM D 123s, E) is 0.01 to 50g
/l 0mln, preferably 0.05 to 30g/l
It is required to be a copolymer obtained by graft copolymerizing a predetermined amount of the unsaturated carboxylic acid or its anhydride (D) or the unsaturated epoxide compound (E) to 10 ml of the unsaturated carboxylic acid or its anhydride (D).

In the ethylene/α-olefin copolymer electrolyte,
If the ethylene content is less than 70 mol%, the rigidity and heat resistance of the IT product will decrease, while if the ethylene content exceeds 95 mol% or the degree of crystallinity by X-rays exceeds 30%, it will be considered a composition. low-temperature impact resistance is not improved.

The graft monomer selected from the unsaturated carboxylic acid or its anhydride (D) or the unsaturated epoxide compound (E) is grafted and copolymerized to the ethylene/α-olefin copolymer (F) to obtain the copolymer (B). ) or (C), various conventionally known methods can be employed. For example, there is a method of melting the ethylene/α-olefin copolymer (F) and adding a graft monomer to carry out graft copolymerization, or a method of dissolving the ethylene/α-olefin copolymer (F) in a solvent and adding a graft monomer to carry out graft copolymerization.

In any case.

In order to efficiently graft copolymerize the graft monomer, it is preferable to carry out the reaction in the presence of a radical initiator. The grafting reaction is usually carried out at 60 to 350°C.
carried out at a temperature of The proportion of the radical initiator used is usually in the range of 0.001 to 1 part by weight per 100 parts by weight of the ethylene/α-olefin copolymer. The radical initiator itself is an organic peroxide, an organic perester, such as benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, di-tert-1-thyl peroxide, 2,5-dimethyl-2,5-di(peroxide benzoate) hexyne- 3,1,4-bis(t
tert-butylperoxyisopropyl)benzene, lauroyl peroxide, tert-butyl peracetate, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexyne-3%2I5-dimethyl-2
,5-di(tert-butylperoxy)hexane.

tert-butylperbenzoate, tert-butylperphenylacetate, tert-butylperisobutylene)* tert-butylperu-5ea-octoate.

tert-butyl perbivalate, cumyl perpivalate and tert-butyl perdiethyl acetate, sono and other aso compounds 1 such as azobisisobutytetranitrile,
There is dimethylazoin butyrate. Among these are dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexyne-3,2,5-dimethyl-2,5
-di(tert-butylperoxy)hexane, 1.4
Dialkyl peroxides such as -bis(tert-butylperoxyisopropyl)benzene are preferred.

The thermoplastic polyester composition of the present invention comprises 50 to 98 parts by weight, preferably 60 to 94 parts by weight of the thermoplastic polyester (A), and the carboxylic acid copolymer (B).
) 1 to 49 parts by weight, preferably 3 to 37 parts by weight, and 1 to 49 parts by weight, preferably 3 to 37 parts by weight of the epoxy copolymer (c).

If the amount of thermoplastic polyester (A) is less than 50 parts by weight, the rigidity and heat resistance of the ff1t product will be impaired. If the amount of carboxylic acid copolymer tB) is less than 1 part by weight, the low-temperature impact resistance will not be improved. On the other hand, if it exceeds 49 parts by weight, rigidity and heat resistance will decrease. If the amount of the epoxy copolymer (C) is less than 1 part by weight, low-temperature impact resistance will not be improved, while if it exceeds 49 parts by weight, rigidity and heat resistance will decrease.

To obtain the thermoplastic polyester of the present invention, a thermoplastic polyester, a carboxylic acid copolymer (B)
and the epoxy copolymer (C) within the above-mentioned range using various known methods 1, such as Henschel mixer, ■-blender, ribbon blender, tumbler blender, etc., then -
Screw extruder, multi-screw extruder, Nigu, Banbury mixer
For example, a melt mixing method may be adopted.

In addition to the above-mentioned components, the thermoplastic polyester FF1L product of the present invention contains a heat-resistant stabilizer and a weather-resistant stabilizer.

Nucleating agents, lubricants, slip agents, antistatic agents, flame retardants, pigments,
Dyes, mold release agents, glass powder, glass flakes, glass fibers, carbon fibers, potassium titanate fibers, reinforcing materials such as mica, calcium carbonate, calcium sulfate, talc, clay, ferrite, barium sulfate, paper waste, cotton waste,
Inorganic or organic fillers such as wood flour may be added to the extent that the purpose of the present invention is not impaired.

Further, in order to improve the rigidity, heat-resistant rigidity, impact resistance, coefficient of linear expansion, etc. of the thermoplastic polyester composition of the present invention, polycarbonate, polyamide.

Other thermoplastic resins such as phoryphenylene oxide, phorysulfone, polyaryl), ABs, etc. may be added to the extent that the object of the present invention is not impaired.

Further, when adding the above-mentioned filler and thermoplastic resin such as polycarbonate or polyamide, it is preferable to add the above-mentioned filler after obtaining the above-mentioned composition in advance because it is more effective.

〔Effect of the invention〕

The thermoplastic polyester composition of the present invention is an M alloy or thermoplastic polyester obtained by adding a base combination of an α-olefin and a glycidyl ester of an α,β-unsaturated acid and a hyethylene copolymer to a thermoplastic polyester. Compared to conventional compositions such as compositions in which an ethylene/α-olefin copolymer grafted with an unsaturated carboxylic acid or its anhydride and a polyepoxy compound are added and mixed, impact resistance at room temperature is improved. It has excellent impact resistance at low temperatures, melt flowability (moldability), as well as rigidity, heat resistance, and gloss.

Exterior panels for automobiles that also have notch impact resistance.

Suitable for automobile parts such as bumpers, foil covers, instrument panels, air spoilers, sight shields, seat packets, mudguards, etc., industrial parts such as power tool housings, electrical appliance parts, helmets, ski boots, housings for various types of OA machines, etc. It can be used for

〔Example〕

Next, the present invention will be explained in more detail with reference to examples, but the present invention is not limited to these examples in any way unless the gist thereof is exceeded.

Example 1 MFRTT) 20g/110m1n (AST D I2
3B, T) polybutylene terephthalate (trade name Toshi PBT, 1a01-XO6, manufactured by Toshi Shiku Co., Ltd.): P
BT) 80 parts by weight, MFRfE): 0.1 g
/l 0mln, oxidation content: 81 mol%, crystallinity = 3%, melting point: 48°C, maleic anhydride graft amount:
iwt% graft modified ethylene propylene random copolymer (MAR/EPC) 5 parts by weight, ethylene content 8? Weight %, containing glycidyl methacrylate ff111
Weight% and MFR (P) 3jg/l 0mln (AS
Intrinsic viscosity [η”: J
: 0.75dj? /g polycarbonate (trade name Yojin Panrai) L-1250, manufactured by Kijin Kasei Co., Ltd.:
pc): io parts by weight after mixing with a Henschel mixer,
The mixtures were melt-mixed using a twin-screw extruder (extrusion temperature: 230°C) to obtain Composition 1-■. MFRTT) (A
STM D 123B, T) is 8. OK/10m
It was in. Next, a test piece for measuring physical properties was molded using an injection molding machine using the Mll metal. The physical properties of the test piece were evaluated by the following method.

Bending test: ASTM D 790 Izot impact strength Ckq・Shin1: Based on ASTM p 256, measurement temperature -30°C
I went there.

Heat distortion temperature: ASTM D 64B, load 4.61g
/cm2 The results are shown in Table 1.

Comparative Example 1 Instead of MAHIPC used in Example 1, MFR: 0
．． Except for using ethylene-propylene random copolymer (GPC) with 48/10 m1n, ethylene content = 81 mol%, crystallinity: 5%, melting point: 48°C.

The procedure was carried out in the same manner as in Example 1 to obtain Composition 1-■. The MFR (T) of this composition is 4. The results of Og/l 0mln are shown in Table 1.

Example 2 PBT used in Example 1: 80 parts by weight, EGM: 10 parts by weight, and MF R+Ilj: 0.2 g710 m
in, ethylene content 91mol%, crystallinity 17(
, melting point 72-C, and 10 parts by weight of graft-modified ethylene/1-butene random copolymer (MAR-EBC) containing 1% by weight of maleic anhydride graft fi were mixed in a Henschel mixer, and then mixed in a twin-screw extruder (extrusion temperature 230°C) to obtain Composition 1-■. Composition - MFR of ■ (T
) was 5g/10mln. The physical property measurement results are the first
Shown in the table.

Comparative example 2 Instead of MAR-EBC used in Example 2.

MFR (E): 3.6g/l 0mtn, ethylene content = 91a + o1%, crystallinity: 17%, and melting point = 72 ° C. Same as Example 2 except for using ethylene/1-butene random copolymer A composition -■ was obtained.

The MFR (T) of this composition was 1.0 g/10 m1n.

The results are shown in Table 1.

Example 3 Intrinsic viscosity of o-chlorophenol at 25°C [η)
: 0.68 dl/g polyethylene terephthalate =
80 parts by weight, gGM used in Example 1: 10 parts by weight, and MAR-11ePC used in Example 1: 10 parts by weight were mixed in a Henschel mixer, and then melted in a twin screw extruder (extrusion temperature 260"C). Composition-V was obtained by mixing. The MFR of this composition was 16.0 g/l 0 mtn (at26
The following procedure was carried out in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 3 Comparative Example 1 was used instead of MAt (-RPC) used in Example 3.
Composition-4 was obtained in the same manner as in Example 3, except that EPc used in Example 3 was used. The MFR of this composition is 9.0 g/l
It was 0mln (at 260°C, 2160g).

The results are shown in Table 1.

The physical property data of Example 3 and Comparative Example 3 are as follows.

This is the value after annealing at 150"C for 1 hour.

Claims (1)

[Claims] (1) (a) Thermoplastic polyester (A) 50 to 9
8 parts by weight, (b) unsaturated carboxylic acid or its anhydride (D) unsaturated carboxylic acid or its anhydride/α-olefin copolymer containing 0.05 to 30% by weight (B) 1 to 49 parts by weight, and (c) unsaturated epoxide compound (
E) Unsaturated epoxide compound/α-olefin copolymer (C) 1 to 4 with a content of 0.05 to 30% by weight
9 parts by weight, and at least one of the α-olefin copolymer (B) or (C) has an ethylene content of 70 to 95 mol% and an X-ray crystallinity of 30.
% or less of an ethylene/α-olefin copolymer (F) and an unsaturated carboxylic acid or its anhydride (D) or an unsaturated epoxide compound (E). Plastic polyester composition.