JPH04164960A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To prepare the title compsn. having an improved compatibility between two polymers blended and an improved impact resistance by blending a specific modified olefin elastomer with a polyamide. CONSTITUTION:2-70wt.% modified olefin elastomer obtd. by graft polymerizing 0.01-30 pts.wt. glycidyl compd. of the formula (wherein R is H or 1-6C alkyl; Ar is a 6-20C arom. hydrocarbon group having at least one glycidyloxy group; and n is an integer of 1-4) onto 100 pts.wt. olefin elastomer comprising 5-95wt.% ethylene units and 95-5wt.% other alpha-olefin units is blended with 30-98wt.% polyamide.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a thermoplastic resin composition containing a modified olefin elastomer and a polyamide, in particular a thermoplastic resin composition in which the polyamide and the olefin elastomer are well compatible,
The present invention relates to a thermoplastic resin composition having excellent mechanical properties such as impact resistance.

[Conventional technology]

Polyamide resin is lightweight, heat resistant, chemical resistant,
It is widely used as an engineering plastic due to its excellent workability and mechanical strength. However, polyamide resins have the disadvantage of being inferior in impact resistance, tensile properties, and the like.

Therefore, with the aim of improving the impact resistance of polyamide, various compositions have been proposed in which polyamide is blended with modified polyolefin, modified olefin elastomer, and the like.

Japanese Patent Publication No. 55-44108 discloses one phase containing a polyamide matrix with a number average molecular weight of at least 5000 and a polyamide matrix having a number average molecular weight of 0.01 to 1. In a reinforced thermoplastic resin composition comprising from 1 to 40% by weight of a specific branched and linear polymer phase having a particle size in the range of , discloses a method using a modified polyolefin or a modified olefin elastomer (which may contain other saturated monomers) as a specific branched or linear polymer having a site that adheres to the polyamide matrix. ing.

Further, JP-A No. 60-219257 discloses a thermoplastic resin composition comprising (A) 99.5 to 60% by weight of a polyamide resin and (B) 0.5 to 40% by weight of an ethylene copolymer. B) Ethylene copolymer, (a) 55-94% by weight of ethylene, (b) 5-40% by weight of a specific alkoxyalkyl acrylate, (C) 0.5-1.5% by weight of maleic anhydride, and ( dl glycidyl methacrylate and/or glycidyl acrylate 0.5-1.
5% by weight, one or more copolymers of (a), (b) and FC) or a terpolymer obtained by polymerizing (a), (bl and (d)) A thermoplastic resin composition is disclosed that is characterized by certain features.

[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 compatibility between polyamide and modified polyolefin is not sufficient.

Therefore, it is an object of the present invention to provide a thermoplastic resin composition in which polyamide 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 lead olefins with a specific glycidyl compound having an acrylamide group and an epoxy group, and a polyamide elastomer. It was discovered that a composition containing polyamide and a modified olefin elastomer is well compatible with each other, and the mechanical properties of the polyamide, particularly impact resistance, are improved, and the present invention was conceived based on this finding.

That is, the thermoplastic resin composition of the present invention comprises (i) an olefin elastomer 1 consisting of 5 to 95% by weight of ethylene and 95 to 5% by weight of α-olefin other than ethylene;
00 parts by weight, Gi) 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) polyamide 30 to 98%.
% 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 means a copolymer rubber of ethylene and one or more olefins other than ethylene, such as propylene, l-butene, -hexene, and 4-methyl-pentene. do.

The above-mentioned copolymer rubbers of ethylene and one or more 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 olefin elastomer is 5 to 95% by weight, preferably 10 to 90% by weight. Ethylene content 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 More preferred ranges are 60 to 70 mol% of ethylene repeating units and 30 to 40 mol% of propylene thread repeating units.

Also, EPR melt flow rate) (MPR, 230
℃, 2.16 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 A more preferable range is 60 to 80 mol% of ethylene repeating units and 20 to 40 mol% of butene thread repeating units.
It is mole%.

In addition, the EBR melt flow rate (VFR, 230°
C12, 16kg load) is 0. It is preferably within the range of O1 to 50g/10 minutes, more preferably 0.5 to 3
0 g/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 unit content is 1-10 mol%. A more preferable range is 50 to 60 mol% of ethylene repeating units,
The propylene repeating units are 40 to 50 mol%, and the diene thread repeating units are 3 to 6 mol%.

Furthermore, the melt flow rate (MFR, 23
0°C, 2,16kg load) is 0.01~50g/10
Preferably, it is within the range of 0.1 minutes, more preferably 0.1 minutes.
~30g 710 minutes.

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 winter olefins such as methylpentene-1, non-elastomeric copolymers of ethylene and propylene or other tooolefins, or two of these complementary olefins.
It is possible to use more than one type of non-elastomeric copolymer, or a blend of these homopolymers, copolymers, or a blend of a homopolymer and a copolymer.

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. Mixed amount of polyolefin: 80% by weight
If it exceeds this, it will lose its properties as an elastomer.

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):
The following can be mentioned.

(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 one phenolic hydroxyl group? 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, ebiodohydrin, 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. The reaction time and temperature are 10 minutes to 3 hours at 20 to 90''C, more preferably 30 minutes to 2 hours at 40 to 70''C.

Such modification (graft polymerization) of an olefin elastomer with a glycidyl compound can be carried out by either a solution method or a melt mixing 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 to a temperature of 180 to 300°C to melt them. While stirring, knead for 0.1 to 20 minutes.

In addition, in the case of a solution method, the above starting materials are dissolved in an organic solvent such as xylene, and a
Do this after stirring for a while. In either case, a conventional radical polymerization catalyst can be used as a catalyst, 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-butylberoxypivale, t,2,5-dimethyl-2,5-ditertiary-butylperoxyhexine, and diazo such as azobisisobutyronitrile. Compounds etc. are preferred. The amount of catalyst added is 0.1 to 10 parts by weight per 100 parts by weight of the modified glycidyl compound. In the present invention, a phenolic antioxidant may be added during the graft reaction. However, if a radical polymerization catalyst is not added, it is preferable not to add it.

The blending ratio of the glycidyl compound (Gi) is the same as (i) above.
0.0% per 100 parts by weight of olefin elastomer.
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 part 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, the polyamide (b) includes hexamethylene diamine, decamethylene diamine, dodecamethylene diamine, 2.2.4- or 2.4.4. -) dimethylhexamethylenediamine, 1.3- or 1.4-
Aliphatic, cycloaliphatic or aromatic diamines such as bis(aminomethyl)cyclohexane, bis(p-aminocyclohexylmethane), m- or p-xylylene diamine and adipic acid, speric acid, sebacic acid, cyclohexane Polyamides prepared from dicarboxylic acids, aliphatic, alicyclic or aromatic dicarboxylic acids such as terephthalic acid and isophthalic acid; amino acids such as 6-aminocaproic acid, 11-aminoundecanoic acid and 12-aminododecanoic acid; Examples include polyamides produced from carboxylic acids, polyamides produced from lactams such as ε-caprolactam and ω-dodecalactam, copolyamides made of these components, and mixtures of these polyamides. Specifically, nylon 6, nylon 66, nylon 610, nylon 9, nylon 6766, nylon 6
6/610, nylon 6/11, nylon 6/12,
Examples include nylon 12, nylon 46, and amorphous nylon. Among these, nylon 6 and nylon 66 are preferred because of their good rigidity and heat resistance.

Although the molecular weight is not particularly limited, it usually has a relative viscosity of 77,
(measured in JISK6810.98% sulfuric acid) or 0.
Polyamides with a rating of 5 or more are used, and among them, polyamides with a rating of 2.0 or more are preferred because they have excellent mechanical strength.

The blending ratio of the above-mentioned (al-modified olefin elastomer and (bl polyamide) is such that (a) the modified olefin-based elastomer is 2 to 70% by weight, preferably 10% by weight.
-40% by weight (98-30% by weight of bl polyamide, preferably 90-60% by weight).

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

The thermoplastic resin composition of the present invention can be further modified with various additives such as inorganic fillers, heat stabilizers, antioxidants, light stabilizers, flame retardants, plasticizers, antistatic agents, etc. It can be added as appropriate.

Such (aJ modified olefin elastomer and (
b) The thermoplastic resin composition of the present invention consisting of polyamide, (al-modified olefin elastomer, (b) polyamide and various additives added as necessary) are processed using a -screw extruder or a twin-screw extruder. , Pan Bali mixer, mixed roll,
200-300°C1 using a crosstalk machine such as Brabender
Preferably, it can be obtained by heating and kneading in a molten state at 250 to 280°C.

[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 polyamide are mixed to form a thermoplastic resin composition.

As a result, impact resistance, which is a disadvantage of polyamide, has been 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 polyamide. 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.

111 Olefin elastomer/ethylene-butene copolymer rubber/EBR [butene content 80%, melt flow rate (230°C 12,16
kg load) 1.5 g/10 minutes] Ethylene-propylene copolymer rubber: EPR [propylene content 70%,
Melt flow rate (230°C, 2.16kg load)
) 1.7 g710 minutes] [2] Modifying monomer ・AXE: Glycidyl compound represented by the following chemical formula [manufactured by Kanekabuchi Chemical Co., Ltd.] ・MAH: Maleic anhydride [3] Radical force generator ・POX: Perhexine 2-5B (manufactured by NOF ■)
[41 Polyamide Nylon-6: Ny-6 [Manufactured by Unitika ■, A1030BRL] ・Nylon-66= Ny-66■: (Manufactured by ICI, Maranyl A125)
Ny-66■: [Manufactured by Toshi■, Amiran 3001N]
- Amorphous nylon: AmNy: manufactured by CEMS, XE 3038) Examples 1 to 6, Comparative Examples 1 to 5 Olefin elastomer, various modifying monomers shown in Table 1, and amounts shown in Table 1 were tri-blended with a radical generator using a Henschel mixer, and 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 polyamides shown in Table 1 were mixed in the proportions shown in Table 1.
250°CC120Orp by mmφ twin screw extruder
The mixture was kneaded to obtain a thermoplastic resin composition.

The melt flow rate, Izot impact strength at 23°C and -30°C, flexural modulus, tensile yield strength, tensile elongation at break, and heat distortion temperature 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 about 50 μs. Then, the IR spectrum was measured, and the peak of the expansion and contraction of the C-〇 bond of AXE (1648 cm-') and one of the peaks (840 cm-1) specific to Aitu Tactical PP were detected.
It was calculated from the ratio of

■For MAR: 50% modified olefin elastomer
It was pressed to a thickness similar to that of a cape, and the IR spectrum was measured.
m-') and one of the peaks (840 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 JTS K6767.

(7) Heat distortion temperature: Measured according to JIS K7207.

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

On the other hand, the thermoplastic resin compositions of Comparative Examples 1 to 3, which were blends of polyamide and unmodified olefin elastomer, had poor impact resistance, tensile yield strength, and tensile elongation at break. Comparative Examples 4 to 6 in which polyamide and olefin elastomer modified with maleic anhydride were blended.
The thermoplastic resin compositions had poorer impact resistance than the thermoplastic resin compositions of the corresponding examples.

This means that the olefin elastomer modified with maleic anhydride has a higher
This is thought to be because although the compatibility with polyamide 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 composition of the present invention is
It consists of an olefin elastomer modified with a specific glycidyl compound containing an acrylamide group and an epoxy group, and a polyamide.

For this reason, the properties of polyamide such as heat resistance, chemical resistance,
It has significantly improved impact resistance, tensile properties, etc. without impairing processability, mechanical strength, etc.

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 (1)

[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 polyamide.