JPH04164955A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To compatibilize an olefin elastomer comprising ethylene units and other alpha-olefin units with a polyester to thereby give a thermoplastic resin compsn. excellent in mechanical properties such as impact strength by graft polymerizing a specific glycidyl compd. onto the olefin elastomer and blending the resulting modified olefin elastomer with the polyester. CONSTITUTION:2-70wt.%, pref. 10-40wt.%, modified olefin elastomer [obtd. by graft polymerizing 0.01-30 pts.wt., pref. 0.1-10 pts.wt., glycidyl compd. of the formula (wherein R is H or a 1-6C alkyl group; Ar is a 6-20C arom. hydrocarbon group contg. at least one glycidyloxy group; and n is 1-4) onto 100 pts.wt. olefin elastomer having an ethylene content of 5-95wt.%, pref. 10-90wt.%, and a crystallinity of 40wt.% or lower] is blended with 30-98wt.%, pref. 90-60wt.%, polyester to give a thermoplastic resin compsn.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a thermoplastic resin composition containing a modified olefin elastomer and a polyester, in particular a thermoplastic resin composition in which the polyester and the olefin elastomer are well compatible, The present invention relates to a thermoplastic resin composition having excellent mechanical properties such as impact resistance. [Prior Art] Polyesters such as polyethylene terephthalate and polybutylene terephthalate are widely used as engineering plastics because of their excellent heat resistance and mechanical strength. However, polyester has the drawback of being inferior in impact resistance, tensile properties, and the like.

Therefore, in order to improve the impact resistance of polyester,
Various compositions have been proposed in which polyester is blended with modified polyolefins, modified olefin elastomers, and the like.

Japanese Patent Publication No. 58-47419 discloses that 70 to 99% of terephthalic acid is added to 100 parts by weight of a saturated polyester consisting of a dicarboxylic acid component containing 40 mol% or more of terephthalic acid and a diol component and having an intrinsic viscosity of 0.5 to 3.0. .5
Weight%, glycidyl methacrylate 0.5-20% by weight
and copolymer 1 consisting of 0 to 0.3% by weight of vinyl acetate.
A resin composition obtained by melt-mixing up to 150 parts by weight is disclosed.

JP-A No. 60-219254 discloses a thermoplastic resin composition comprising (A) 99.5 to 60% by weight of a saturated polyester resin and (B) 0.5 to 40% by weight of an ethylene copolymer. B) The ethylene copolymer is (a)
55-94% by weight of ethylene, 5-40% by weight of (bl specific alkoxyalkyl acrylate), 0.5-1.5% by weight of (C1 maleic anhydride and (d) 0.5-1% glycidyl methacrylate and/or glycidyl acrylate)
．． Among 5% by weight, one or more copolymers of (a), (b) and (C), or a terpolymer formed by polymerizing (a), (b) and (d) Disclosed is a thermoplastic resin composition characterized in that it is a composite.

JP-A-1-193351 discloses that α
- Discloses an aromatic polyester composition containing 0.1 to 60 parts by weight of an olefinic polymer consisting of an olefin and a glycidyl ester of an α-unsaturated acid.

JP-A-1-236266 discloses (A) 100 parts by weight of a thermoplastic polyester resin, (B) a vinyl cyanide compound,
1 to 100 parts by weight of one type of homopolymer or two or more types of copolymers selected from acrylic esters, methacrylic esters, aromatic vinyl compounds, etc., and (C) α-olefin, α, B- An olefin copolymer consisting of a glycidyl ester of an unsaturated acid, or the above-mentioned lefin copolymer, a vinyl cyanide compound, an acrylic ester,
A thermoplastic polyester resin composition containing 0.5 to 80 parts by weight of a graft copolymer grafted with a methacrylic acid ester, an aromatic vinyl compound, etc. is disclosed.

[Invention or problem to be solved]

However, these thermoplastic resin compositions have a problem in that physical properties such as impact resistance are not necessarily sufficiently improved because the polyester and modified polyolefin are not sufficiently compatible.

Therefore, an object of the present invention is to provide a thermoplastic resin composition in which polyester and olefin elastomer are well compatible and have excellent mechanical properties such as impact resistance.

[Means to solve the problem]

As a result of intensive research in view of the above objectives, the present inventors have developed a modified olefin elastomer obtained by modifying a copolymer elastomer of ethylene and other common olefins with a specific glycidyl compound having an acrylamide group and an epoxy group, and a polyester elastomer. The inventors have discovered that a composition containing polyester and a modified olefin elastomer is well compatible with each other, and the mechanical properties of the polyester, particularly impact resistance, are improved, and the present invention has been conceived.

That is, the thermoplastic resin composition of the present invention contains (i) 5 to 95% by weight of ethylene and 9% of a secondary olefin other than ethylene.
Olefin elastomer 10 consisting of 5 to 5% by weight
With respect to 0 parts by weight, GO the following general formula: (wherein R is H or an alkyl group having 1 to 6 carbon atoms,
Ar is an aromatic hydrocarbon group having at least one glycidyloxy group and having 6 to 20 carbon atoms, and n is an integer of 1 to 4.
2 to 70% by weight of a modified olefin elastomer obtained by graft polymerizing parts by weight, and (b) 30 to 9% of polyester.
8% by weight.

The present invention will be explained in detail below.

In the present invention, (a) modified olefin elastomer is obtained by modifying (i) olefin elastomer with (2) a specific glycidyl compound having an acrylamide group and an epoxy group.

The above (i) olefin elastomer refers to a copolymer rubber of ethylene and one or more α-olefins other than ethylene, such as propylene, l-butene, 1-hexene, and 4-methyl-pentene. means.

The copolymer rubbers of ethylene and one or more common olefins other than ethylene are typically ethylene-butene copolymer rubber (EBR), ethylene-propylene copolymer rubber (EPR), and Examples include ethylene-propylene-diene copolymer rubber (EPDM). As the diene in the ethylene-propylene-diene copolymer (EPDM), non-conjugated dienes such as dicyclopentadiene, 1,4-hexadiene, cyclooctadiene, methylene norbornene, or conjugated dienes such as butadiene and isoprene are used. be able to.

The content of ethylene in the above-mentioned reflex elastomer is 5 to 95% by weight, preferably 10 to 90% by weight. Ethylene content is less than 5% by weight or 95% by weight
If it exceeds % by weight, it becomes difficult to express the properties as an elastomer. The degree of crystallinity of such an olefin elastomer is usually 40% by weight or less.

The ethylene-propylene copolymer rubber (EPR) used in the present invention has a content of repeating units derived from ethylene of 50 to 80 mol% and a content of repeating units derived from propylene of 20 to 50 mol%. It is preferable that A more preferable range is 60 to 70 mol% of ethylene repeating units and 30 to 40 mol% of propylene repeating units.

In addition, EPR melt flow rate (MFR, 230°
C12, 16 kg load) is preferably within the range of 0.01 to 50 g/10 minutes, more preferably 0.5 to 3
0 g/10 minutes.

The ethylene-butene copolymer rubber (EBR) used in the present invention has a content of repeating units derived from ethylene of 50 to 90 mol% and a content of repeating units derived from butene of 10 to 50 mol%. It is preferable that More preferable ranges are 60 to 80 mol% of ethylene repeating units and 20 to 40 mol% of butene thread repeating units.
It is mole%.

In addition, EBR melt flow rate (MFR, 230℃
, 2.16 kg load) is preferably within the range of 0.01 to 50 g/10 minutes, more preferably 0.5 to 50 g/10 minutes.
30g/10 minutes.

Furthermore, ethylene-propylene- used in the present invention
The diene copolymer (EPDM) has a content of repeating units derived from ethylene of 40 to 70 mol%, a content of repeating units derived from propylene of 30 to 60 mol%, and a repeating unit derived from diene. It is preferable that the content of the units is 1 to 10 mol%. A more preferable range is 50 to 60 mol% of ethylene repeating units,
The proportion of propylene repeating units is 40 to 50 mol%, and the proportion of diene yarn repeating units is 3 to 6 mol%.

Furthermore, the melt flow rate (MFR, 23
0°C, 2,16kg load) is 0601~50g/10
It is preferably within the range of 0.1 min, more preferably 0.1 min.
~30g710min.

Ethylene-propylene copolymer (EPR), ethylene-butene copolymer rubber (EBR) used in the present invention
and ethylene-propylene-diene copolymer (EPDM
) consists basically of the above-mentioned repeating units or is derived from other α-olefins, such as 4-methylpentene-1, to the extent that the properties of these copolymers are not impaired. Other repeating units such as repeating units may be included up to a proportion of 10 mol % or less.

Note that as the olefin elastomer (i) mentioned above, a mixture of the olefin elastomer and a crystalline polyolefin at a ratio of 80% by weight or less based on the total 100% by weight of both may be used.

Crystalline polyolefins that can be used in the method of the present invention include ethylene, propylene, butene-1, hexene-1,4-
Homopolymers of lead olefins such as methylpentene-1, non-elastomeric copolymers of ethylene and propylene or other common olefins, or two of these common olefins.
Non-elastomeric copolymers of more than one species, homopolymers and copolymers, copolymers and copolymers, and blends of homopolymers and copolymers can be used.

When mixing crystalline polyolefin, the mixing amount is 10 olefinic elastomers and 10 crystalline polyolefins.
Defining 0% by weight, it is 80% by weight or less, preferably 50% by weight or less. If the amount of polyolefin mixed exceeds 80% by weight, the properties as an elastomer will be lost.

In addition, in the present invention, (1) the modifying monomer has the following general formula (
1): (wherein R is H or an alkyl group having 1 to 6 carbon atoms,
Ar is an aromatic hydrocarbon group having 6 to 20 carbon atoms and having at least one glycidyloxy group, and n is 1 to 4.
It is a glycidyl compound represented by (representing an integer of ).

Preferred glycidyl compounds include the following general formula (2):
Can you list what is expressed as?

(In the formula, R is H or an alkyl group having 1 to 6 carbon atoms,
n represents an integer of 1 to 4. ) Such glycidyl compounds are disclosed in, for example, JP-A-60-1
As shown in No. 30580, it can be manufactured by the following method.

First, an aromatic hydrocarbon having at least one phenolic hydroxyl group and an alkyl ether derivative of N-methylol acrylamide, N-methylol methacrylamide, or N-methylol methacrylamide (
Hereinafter, these are referred to as N-methylolacrylamides) by condensing with an acid catalyst, the following general formula (3) (wherein R is H or an alkyl group having 1 to 6 carbon atoms,
Ar' has at least one hydroxyl group and has 6 carbon atoms
~20 aromatic hydrocarbon groups, and n represents an integer of 1 to 4. ) is produced.

Is there any particular restriction on the aromatic hydrocarbon having at least I or more phenolic hydroxyl groups? For example, phenol, 0-cresol, m-cresol, p-cresol, 2,6-xylenol, 2,4-xylenol, 0
- Phenolic compounds such as chlorophenol, m-chlorophenol, 0-phenylphenol, p-chlorophenol, 2゜6-diphenylphenol, polyphenolic compounds such as hydroquinone, catechol, phloroglucinol, 1-naphthol, 2 - Naphthol, 9
Examples thereof include polycyclic hydroxy compounds such as -hydroxyanthracene, bisphenols such as 2,2-bis(4-hydroxyphenyl)propane (bisphenol-A), and bis(4-hydroxyphenyl)methane.

Next, by glycidylating the hydroxyl group of the compound represented by the above general formula (3), a glycidyl compound represented by the general formula (1) can be obtained.

This glycidylation is preferably carried out by carrying out an addition reaction between the compound represented by the general formula (3) and epihalohydrin, followed by dehydrohalogenation with a caustic alkali.

The addition reaction with epihalohydrin is carried out using a phase transfer catalyst.

As the epihalohydrin, epichlorohydrin, epibromohydrin, epiiodohydrin, etc. can be used.

Examples of phase transfer catalysts include quaternary ammonium salts such as tetrabutylammonium bromide, trioctylmethylammonium chloride, benzyltriethylammonium chloride, and quaternary phosphonium salts such as tetraphenylphosphonium chloride and triphenylmethylphosphonium chloride. can be used.

The amount of the phase transfer catalyst used is 0.01 to 100 mol%, based on 100 mol% of the compound represented by general formula (3).
It is preferable that it is in the range of . A particularly preferred amount of phase transfer catalyst used is 0.05 to 10 mol%. The reaction time and temperature are 5 minutes to 2 hours at 50 to 120°C, more preferably 10 to 30 minutes at 80 to 110°C.

Subsequently, dehydrohalogenation is performed using caustic alkali.

As the caustic alkali, caustic soda, caustic potash, lithium hydroxide, etc. can be used. These can be used as solids or as aqueous solutions. Further, as a catalyst for dehydrohalogenation, the same one as the above-mentioned phase transfer catalyst can be used. Catalysts other than the above-mentioned phase transfer catalysts include crown ethers, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, and the like.

The amount of the caustic alkali to be used is preferably equimolar to the compound represented by the general formula (3). More preferably, 1.1 to 1.5 times the mole is used. In addition, the reaction time and reaction temperature are 10 minutes to 3 hours at 20 to 90°C.
More preferably, the temperature is 40 to 70°C for 30 minutes to 2 hours.

Such modification (graft polymerization) of an olefin elastomer with a glycidyl compound can be carried out by either a solution method or a melt-kneading method.

In the case of the melt-kneading method, the olefin elastomer, the above-mentioned glycidyl compound for modification, and a catalyst if necessary are put into an extruder or twin-screw kneader, etc., and heated at 180 to 300°C.
The mixture is heated to a temperature of 100 to melt the mixture, and then kneaded for 0.1 to 20 minutes. In addition, in the case of a solution method, the above starting material is dissolved in an organic solvent such as xylene, and 0.1 to 10
Do this after stirring for 0 hours. In either case, ordinary radical polymerization catalysts can be used as catalysts, such as benzoyl peroxide, lauroyl peroxide, di-tert-butyl peroxide, acetyl peroxide, tert-butyl peroxybenzoic acid, dicumyl peroxide, Peroxides such as peroxybenzoic acid, peroxyacetic acid, tert-butylperoxypivalate, 2,5-dimethyl-2,5-ditertiary-butylperoxyhexine, diazo compounds such as azobisisobutyronitrile, etc. is preferred. The amount of the catalyst added is about 0.1 to 10 parts by weight per 100 parts by weight of the modified glycidyl compound. In the present invention, a phenolic antioxidant can be added during the graft reaction. However, if a radical polymerization catalyst is not added, it is preferable not to add it.

Based on 100 parts by weight of the 60 glycimoolefin elastomer, 0.
01 to 30 parts by weight, preferably 0.1 to 10 parts by weight. If the amount of the glycidyl compound is less than 0.01 parts by weight, it is difficult to achieve a high grafting rate, and if it exceeds 30 parts by weight, the molecular weight of the modified olefin elastomer obtained will decrease.

In the present invention, (b) polyester is generally a thermoplastic resin made of saturated dicarboxylic acid and saturated dihydric alcohol, such as polyethylene terephthalate, polypropylene terephthalate, polytetramethylene terephthalate (polybutylene terephthalate), polyhexamethylene terephthalate, polyester Examples include cyclohexane-1,4-dimethylol terephthalate and polyneopentyl terephthalate. Among these, polyethylene terephthalate and polybutylene terephthalate are particularly preferred.

The above polyester has an intrinsic viscosity [η] of 0.30 to 1.8.
and a concentration of terminal carboxyl groups of 10 to 200 m equivalents/kg. Here, the intrinsic viscosity [η) (
di/g) is 25 in 0-chlorophenol solvent.
It was determined from the solution viscosity measured at °C.

In the case of polyethylene terephthalate, the intrinsic viscosity [η] is 0.30 to 1.2, and the terminal carboxyl group concentration is 10 to 1.2.
Preferably it is 200 m equivalents/kg. The terephthalic acid component in polyethylene terephthalate may be substituted with an alkyl group, a halogen group, etc., and the glycol component may be 50% by weight in addition to ethylene glycol.
It may also contain other glycols to some extent, such as 1,4-butylene glycol, propylene glycol, hexamethylene glycol, etc.

In addition, in the case of polybutylene terephthalate, the intrinsic viscosity [
η] is preferably 0.30 to 1.8, and the terminal carboxyl group concentration is preferably 1O to 200 m equivalent/kg.

In this case as well, the terephthalic acid component may be substituted with an alkyl group, a halogen group, etc., and the glycol component may contain up to about 50% by weight of other glycols in addition to 1,4-butylene glycol, such as ethylene gelcol, It may contain propylene glycol, hexamethylene gelcol, etc.

The blending ratio of the Cal-modified olefin elastomer as described above and (b) polyester is 2 to 70% by weight, preferably 1% by weight of the (a) modified olefin elastomer.
0 to 40% by weight, and (b) polyester is 98 to 3
0% by weight, preferably 90-60% by weight.

(a) If the modified olefin elastomer is less than 2% by weight ((b) If the polyester is more than 98% by weight), the effect of improving the physical properties such as impact resistance of the polyester by its blending is not sufficient, and (a) ) If the amount of the modified olefin elastomer exceeds 70% by weight ((b) if the amount of polyester is less than 30% by weight), the properties of the polyester will be impaired.

The thermoplastic resin composition of the present invention may have the above composition or may contain fillers such as inorganic fillers and carbon black, and other additives such as heat stabilizers, light stabilizers, and flame retardants for the purpose of modifying the composition. , a plasticizer, an antistatic agent, a foaming agent, a nucleating agent, etc. may be added.

Such (a) modified olefin elastomer, (
b) The thermoplastic resin composition of the present invention comprising polyester, fa) modified olefin elastomer, and (b)
Polyester and various additives added as necessary are mixed using a mixing machine such as a -screw extruder, twin-screw extruder, Pan Bali mixer, mixing roll, Brabender, etc.
C1 Preferably, it can be obtained by heating in a molten state at 240 to 280°C and cross-fertilizing the wire.

[For production]

In the present invention, a modified olefin elastomer modified with a specific glycidyl compound having an acrylamide group and an epoxy group and a polyester are mixed to form a thermoplastic resin composition. For this reason, impact resistance, which is a disadvantage of polyester, is significantly improved.

The reason why such an effect is obtained is not necessarily clear, or a specific glycidyl compound is used as a monomer for modifying the modified olefin elastomer, and this glycidyl compound has acrylamide at one end and acrylamide at the other end. Because it is a monomer that has an epoxy group and also has a benzene ring, it has excellent properties such as reactivity and heat resistance, and a composition of an olefin elastomer modified with such a monomer and a polyester. Therefore, it is thought that this is because the two are well compatible.

〔Example〕

The present invention will be explained in further detail by the following specific examples.

In addition, in each Example and Comparative Example, the following materials and additives were used.

[1] Olefin elastomer/ethylene-butene copolymer rubber: EBR [butene content 80%, melt flow rate (230°C, 2,16
kg load) 1.5 g/10 minutes] Ethylene-propylene copolymer rubber: EPR [propylene content 70%,
Melt flow rate (230°C 12, 16kg load)
1.7 g710 minutes] [21 Modifying monomer AXE: Glycidyl compound represented by the following chemical formula [manufactured by Kanekabuchi Chemical Industry ■] ・MAH: Maleic anhydride [3] radical generator ・POX: Verhexin 2- 5B (manufactured by NOF ■)
[4] Polyester polyethylene terephthalate PET: (TR4550 manufactured by Teijin ■, intrinsic viscosity [η]
0.7] ・Polybutylene terephthalate PBT: (C700ON manufactured by Teijin ■, intrinsic viscosity [η] 1
．． 05) Examples 1 to 9, Comparative Examples 1 to 5 Olefin elastomers, various modifying monomers shown in Table 1, and radical generators in amounts shown in Table 1 were tri-blended using a Henschel mixer. , then in a single-screw extruder with a diameter of 30 mm and L/D=25.
Graft polymerization was carried out by melt-kneading at 0°C and 30 rpm.

The melt flow rate of the modified olefin elastomer thus obtained and the grafting rate of the modifying monomer were measured.

The results are also shown in Table 1.

Next, the above-mentioned modified olefin elastomer and various polyesters shown in Table 1 were mixed in the proportions shown in Table 1.
250°CC120Or by 5mmφ twin screw extruder
A thermoplastic resin composition was obtained by mixing with p.

The melt flow rate, Izot impact strength at 23°C and -30°C, flexural modulus, tensile yield strength, and tensile elongation at break of the thermoplastic resin composition thus obtained were measured.

The results are also shown in Table 1.

(1) MFR: Measured according to JIS K7210.

(2) Grafting ratio of modifying monomer: ■For AXE: Dissolve the modified olefin elastomer in boiling xylene, remove insoluble components, precipitate the dissolved components with methanol, and press this to a thickness of approximately 50 tIn. Then, measure the IR spectrum and find that AXE C=0
The bond expansion/contraction peak (1648an-') and one of the peaks specific to Aitsu Tactical PP (840an-1)
) was calculated from the ratio.

■For MAR: 50% modified olefin elastomer
It was pressed to a thickness of about 1 inch, and the IR spectrum was measured.
It was calculated from the ratio of 0an-') to one of the peaks (84°an-') characteristic of Aitsu Tactical PP.

(3) Izot impact strength: Measured according to JIS K7110.

(4) Flexural modulus: Measured according to JIS K7203.

(5) Tensile yield strength: Measured according to JIS K6767.

(6) Tensile elongation at break: Measured according to JIS K6767.

As is clear from Table 1, the thermoplastic resin composition of the present invention had excellent impact resistance, flexural modulus, tensile yield strength, and tensile elongation at break.

On the other hand, the thermoplastic resin compositions of Comparative Examples 1 to 3, which were blends of polyester and unmodified resin elastomer, had poor impact resistance and tensile elongation at break. Furthermore, the thermoplastic resin compositions of Comparative Examples 4 and 5, which were blends of polyester and an olefin elastomer modified with maleic anhydride, had better impact resistance and tensile elongation at break than the thermoplastic resin compositions of the corresponding examples. was inferior.

This means that the olefin elastomer modified with maleic anhydride has a higher
This is thought to be because although the compatibility with polyester is good, the compatibility is inferior to that of the modified olefin elastomer used in the present invention.

〔Effect of the invention〕

As detailed above, the thermoplastic resin assembly of the present invention is
It consists of an olefin elastomer modified with a specific glycidyl compound having an acrylamide group and an epoxy group, and a polyester.

Therefore, the impact resistance is significantly improved without impairing the heat resistance, mechanical strength, etc., which are the characteristics of polyester.

Such a thermoplastic resin composition of the present invention is suitable as various engineering plastics, particularly as a resin composition for automobile parts, home appliance parts, industrial material parts, packaging materials, and the like.

Claims (2)

[Claims] (1) (a) <i> For 100 parts by weight of an olefinic elastomer consisting of 5 to 95% by weight of ethylene and 95 to 5% by weight of α-olefin other than ethylene, <ii>
The following general formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R is H or an alkyl group having 1 to 6 carbon atoms,
Ar is an aromatic hydrocarbon group having at least one glycidyloxy group and having 6 to 20 carbon atoms, and n is an integer of 1 to 4.
1. A thermoplastic resin composition comprising: 2 to 70% by weight of a modified olefin elastomer obtained by graft polymerizing parts by weight, and (b) 30 to 98% by weight of polyester. (2) In the thermoplastic resin composition according to claim 1,
A thermoplastic resin composition, wherein the polyester is polyethylene terephthalate or polybutylene terephthalate.