JPH0627229B2 - Thermoplastic resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial field of application> The present invention relates to a thermoplastic resin composition having high tear strength and tensile strength, and excellent moldability and flexibility.

<Prior Art> Polyether ester amides having a polyamide repeating unit, a polyether repeating unit and an ester bond in the polymer main chain are known (US Pat. No. 3,044,987). Further, a polyolefin elastomer, which is a composition composed of a polyolefin resin and an ethylene copolymer rubber, is also known (Japanese Patent Publication No. 53-21021 and Japanese Patent Publication No. 53-3).
4210, JP-A-59-58043, JP-A-59-91142).

<Problems to be Solved by the Invention> Polyether ester amide is used for various molding applications because it is excellent in flexibility, transparency and mechanical properties, and burrs and sinks are less likely to occur during molding. There was a problem in productivity because the solidification rate was slow and it was necessary to lengthen the cooling time.

On the other hand, although the polyolefin elastomer is excellent in lightness and flexibility, there are problems that a molded product such as a sink is likely to be deformed at the time of molding, and that tear strength and tensile strength are small.

The present invention has been made for the purpose of solving the above problems and providing a thermoplastic resin composition having excellent tear strength, tensile strength, moldability and flexibility at the same time.

<Means for Solving Problems> As a result, the object of the present invention is to provide an aminocarboxylic acid or lactam having 6 or more carbon atoms, or a salt of diamine and dicarboxylic acid having 6 or more carbon atoms (a), and a number average molecular weight of 300. ~ 6,000
Poly (alkylene oxide) glycol (b), and polyether ester amide (A) derived from dicarboxylic acid (c) having 4 to 20 carbon atoms in an amount of 1 to 99% by weight, polypropylene and vulcanized ethylene It has been found that this can be achieved by providing a thermoplastic resin composition in which the polyolefin elastomer (B) made of a copolymer rubber is blended in a proportion of 99 to 1% by weight.

The configuration of the present invention will be specifically described below.

Examples of the aminocarboxylic acid having 6 or more carbon atoms or lactam or the salt (a) of diamine and dicarboxylic acid having 6 or more carbon atoms in the polyether ester amide (A) of the present invention include ω-aminocaproic acid and ω-aminoenanthic acid. , Ω
-Aminocaprylic acid, ω-aminopelargonic acid, ω-aminocapric acid, 11-aminoundecanoic acid, 12-aminododecanoic acid and other aminocarboxylic acids, or lactams such as caprolactam, enantolactam, capryllactam, laurolactam and hexamethylene Diamine-dicarboxylic acid such as diamine-adipate, hexamethylenediamine-sebacate, hexamethylenediamine-isophthalate, undecamethylenediamine-adipate, 4,4'-diaminodicyclohexylmethane-dodecanedioate Although there are salts, caprolactam, 11-aminoundecanoic acid, 12-aminododecanoic acid are particularly preferable,
These may be used in combination depending on the purpose and use.

Further, it is acceptable to use another amide-forming component as a copolymerization component for the purpose of lowering the melting point of the polyether ester amide or increasing the adhesiveness, as long as it is in a small amount range.

Polyether ester amide (A) of the present invention has a number average molecular weight of 300 to 6,000 poly (alkylene oxide) glycol (b), polyethylene glycol, poly (1,2- and 1,3-propylene oxide) glycol,
Examples include poly (tetramethylene oxide) glycol, poly (hexamethylene oxide) glycol, ethylene oxide / propylene oxide block or random copolymers, ethylene oxide / tetrahydrofuran block or random copolymers, among others, heat resistance and water resistance. Poly (tetramethylene oxide) glycol is preferably used because of its excellent physical properties such as mechanical strength, elastic recovery and the like. The number average molecular weight of poly (alkylene oxide) glycol is 30
Although it can be used in the range of 0 to 6,000, a molecular weight range that does not cause coarse phase separation during polymerization and is excellent in low temperature characteristics and mechanical properties is selected. This optimum molecular weight range depends on the type of poly (alkylene oxide) glycol. different. For example, in the case of polyethylene glycol, 300 to 6,000, particularly preferably
1,000 to 4,000 are 300 to 5,000 in the case of poly (propylene oxide) glycol, particularly preferably 500 to 3,000, and 50 in the case of poly (tetramethylene oxide) glycol.
Those having a molecular weight range of 0 to 3,000, particularly preferably 500 to 2,500 are preferably used.

Examples of the dicarboxylic acid (c) having 4 to 20 carbon atoms in the polyetheresteramide (A) of the present invention include terephthalic acid, isophthalic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid and diphenyl- 4,4'-dicarboxylic acid, diphenoxyethanedicarboxylic acid, aromatic dicarboxylic acid such as sodium 3-sulfoisophthalate,
Alicyclic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, dicyclohexyl-4,4'-dicarboxylic acid, and succinic acid, oxalic acid, adipic acid, sebacic acid, dodecanedioic acid (decane Aliphatic dicarboxylic acids such as dicarboxylic acids) can be mentioned. Especially terephthalic acid, isophthalic acid, 1,4
-Dicarboxylic acids such as dichlorohexanedicarboxylic acid, adipic acid, sebacic acid and dodecanedioic acid are preferably used in terms of polymerizability, color tone and physical properties of the polymer.

If the copolymerization amount of the polyether ester unit derived from poly (alkylene oxide) glycol (b) and dicarboxylic acid (c) in polyether ester amide (A) is too small, flexibility and elastic recovery are lost. On the other hand, if the amount is too large, mechanical properties such as high temperature characteristics and strength tend to be impaired. Therefore, 5 to 90% by weight is preferable in order to obtain the effects of the present invention most significantly.

The method for polymerizing the polyether ester amide (A) is not particularly limited, and a known method can be used. For example,
Aminocarboxylic acid or lactam, or salt of diamine and dicarboxylic acid (a) is reacted with dicarboxylic acid (c) to form a polyamide prepolymer having carboxylic acid groups at both ends, and poly (alkylene oxide) glycol (b) is added thereto. Method of reacting under vacuum, or by charging the compound of the above (a), (b), (c) into a reaction tank, and heating reaction at high temperature in the presence or absence of water at a carboxylic acid terminated polyamide pre A method is known in which a polymer is formed and then the polymerization is allowed to proceed under normal pressure or reduced pressure. In addition, (a), (b),
There is also a method in which the compound (c) is charged into a reaction vessel at the same time, melt polymerization is carried out, and then the polymerization is carried out all at once under a high vacuum. This method is rather preferable because the coloring of the polymer is small.

The polyolefin elastomer (B) in the present invention is a thermoplastic composition comprising polypropylene and a vulcanized ethylene copolymer rubber.

The ethylene-based copolymer rubber means ethylene and α-
It is a copolymer derived from a compound containing olefin as an essential component and optionally a non-conjugated diene.

Here, as α-olefin, poropylene, butene-
1, pentene-1 and 4-methylpentene-1 are mentioned, and among them, propylene and butene-1 are preferably used.

Further, as the non-conjugated diene, dicyclopentadiene (DCPD), 5- (2-methyl-2-butenyl) -2-norbornene, 5-methylene-2-norbornene (MNB),
5-ethylidene-2-norbornene (ENB), methyltetrahydroindene (MTHI), 1,4-hexadiene (1,4-H
D) and the like, among which DCPD, ENB, and 1,4-HD are preferably used.

The copolymerization amount of ethylene in the ethylene copolymer rubber is 20
~ 90 wt%, α-olefin copolymerization amount is 80 ~ 10 wt%
When copolymerizing a non-conjugated diene, 10 parts by weight or less is preferable with respect to 100 parts by weight of ethylene and α-olefin. Polyolefin elastomer (B) is a composition composed of the above-mentioned polypropylene and vulcanized ethylene copolymer rubber, but its compounding ratio is such that if the polypropylene is too small, the moldability is too large, and if it is too large, the flexibility is insufficient. Therefore, the proportion of 10 to 80% by weight of polypropylene and 90 to 20% by weight of vulcanized ethylene copolymer rubber is preferable.

This composition is produced by a known method. That is,
Method of melt blending polypropylene and vulcanized ethylene copolymer rubber, method of melt blending partially vulcanized product of ethylene copolymer rubber and polypropylene (JP-B-53
-21021), a method of dynamically vulcanizing a mixture of polypropylene and an ethylene copolymer rubber to obtain a partially vulcanized product (Japanese Patent Publication No. 53-34210), a mixture of a polypropylene and an ethylene copolymer rubber. Vulcanized dynamically under high shear rate,
Examples thereof include a method of finely dispersing a vulcanized product of an ethylene copolymer rubber in a polyolefin resin (JP-A-59-58043 and JP-A-59-91142).

As a vulcanizing agent, organic peroxide, sulfur, phenol resin,
Phenylene bismaleimide, urethane vulcanizing agent, and diamine vulcanizing agent are preferable, and they can be used in combination with a vulcanization aid.

Here, the ethylene copolymer rubber needs to be vulcanized. If not vulcanized, the mechanical properties tend to be inadequate.

In the present invention, the blending ratio of the polyether ester amide (A) and the polyolefin elastomer (B) is such that (A) is 1 to 99% by weight, preferably 5 to 95% by weight, particularly preferably 10 to 90% by weight.
It is necessary that the content of (B) is 99 to 1% by weight, preferably 95 to 5% by weight, and particularly preferably 90 to 10% by weight. If (A) is less than 1% by weight, the tear strength, tensile strength and moldability of the present invention are not sufficient, and if it exceeds 99% by weight, there is a problem in moldability.

The resin composition of the present invention is preferably melt-kneaded, and a known method can be used as the melt-kneading method. For example, using a Banbury mixer, a rubber roll machine, a single-screw or twin-screw extruder, etc., it is possible to melt-knead at a temperature of usually 100 to 300 ° C. to obtain a resin composition.

In addition, the resin composition of the present invention includes known antioxidants, thermal decomposition inhibitors, UV inhibitors, hydrolysis resistance improvers, colorants (pigments, dyes), antistatic agents, conductive agents, flame retardants, reinforcing agents. Agents, fillers, lubricants, nucleating agents, release agents, plasticizers, process oils, adhesion aids, pressure sensitive adhesives and the like can be optionally contained.

These additives can be added at any time.
For example, a method of adding it to a polyether ester amide and blending it with a polyolefin elastomer, or a method of adding it to a polyolefin elastomer and blending it with a polyether ester amide, or a polyether ester amide, a polyolefin elastomer and an additive. Examples include a method of simultaneously blending. Moreover, you may use these compounding methods together.

<Examples> Unless otherwise specified in the examples, the number of parts means parts by weight.

Reference Example [Production of Polyether Esteramide] Polyether ester amide used in Examples and Comparative Examples
Polymerization of (A) is as follows.

Polymerization of polyetheresteramide (A-1) ω-aminododecanoic acid 81.9 parts, dodecanedioic acid 6.8 parts, and poly (tetramethylene oxide) having a number average molecular weight of 650.
19.3 parts of glycol together with 0.5 part of “Irganox” 1098 (antioxidant) were charged into a reaction vessel equipped with a helical ribbon stirring blade, nitrogen purged, and heated and stirred at 260 ° C. for 1 hour to form a homogeneous transparent solution. Antimony oxide catalyst 0.015
Parts, monobutyl monohydroxytin oxide catalyst 0.015
Parts, 0.005 parts phosphoric acid (tinting inhibitor) was added and brought to a polymerization condition of less than 1 mmHg in 1 hour according to a vacuum program. When reacted for 2.5 hours under these conditions, a viscous colorless and transparent molten polymer was obtained, and when this polymer was discharged as gut into water, it was crystallized and whitened. The obtained polyetheresteramide (A-1) has a relative viscosity (ηr) of 1.81 measured at a concentration of 0.5% in orthochlorophenol at 25 ° C. and a crystal melting point by DSC of 167 ° C.
It was.

Polymerization of polyetheresteramide (A-2) 49.1 parts of ω-aminododecanoic acid, 7.9 parts of terephthalic acid, 48.8 parts of poly (tetramethylene oxide) glycol with a number average molecular weight of 1020, 0.5 part of "Irganox" 1098, trioxide Polymer (A-1) from 0.015 parts of antimony, 0.015 parts of monobutylmonohydroxytin oxide, and 0.005 parts of phosphoric acid
Polymerization was carried out under the same conditions as above to obtain a polyetheresteramide (A-2) having a relative viscosity of 1.93 and a melting point of 154 ° C.

Polymerization of polyetheresteramide (A-3) ω-aminododecanoic acid 27.3 parts, terephthalic acid 5.7 parts, poly (tetramethylene oxide) glycol having a number average molecular weight of 2060 70.5 parts, "Irganox" 1098 0.5 part, trioxide Polymer (A-1) from 0.015 parts of antimony, 0.015 parts of monobutylmonohydroxytin oxide, and 0.005 parts of phosphoric acid
Polymerization was carried out under the same conditions as above to obtain a polyetheresteramide (A-3) having a relative viscosity of 1.92 and a melting point of 145 ° C.

[Production of polyolefin-based elastomer]

The production of the polyolefin-based elastomer (B) used in Examples and Comparative Examples is as follows.

Manufacturing of polyolefin elastomer (B-1) Polypropylene with melting index (230 ℃, 2160g load) of 3.0
20 parts, copolymerization ratio of ethylene / propylene / 5-ethylidene-2-norbornene = 65/30/5, Mooney viscosity (ML
_{1 + 4} , 100 ° C) 40 parts of ethylene copolymer rubber (EPDM) of 80 parts and 0.8 parts of organic peroxide vulcanizing agent dicumyl peroxide are charged into a Banbury mixer having a volume of 3 and 190 ° C, 30 ° C.
Knead at rpm for 10 minutes, and then polyolefin elastomer (B-
1) got.

Production of (B-2) Polypropylene 30 identical to that used in production of (B-1)
Part, EPDM 70 parts and dicumyl peroxide 0.7 parts (B
Kneading was performed under the same conditions as in (-1) to obtain a polyolefin-based elastomer (B-2).

Production of (B-3) Polypropylene 40 identical to that used in production of (B-1)
Part, EPDM 60 parts and dicumyl peroxide 0.6 parts (B
Kneading was performed under the same conditions as in (-1) to obtain a polyolefin-based elastomer (B-3).

Production of (B-4) 100 parts of EPDM identical to that used in production of (B-1), 30 parts of clay, 100 parts of paraffinic process oil with a flash point of 310 ° C.
Parts and 5 parts of titanium dioxide were put into a Banbury mixer having a volume of 10 and kneaded at 100 ° C. and 30 rpm for 30 minutes to obtain a masterbatch (m). 235 parts of masterbatch (m), 33 parts of polypropylene identical to that used to make (B-1), zinc oxide 5
Parts, stearic acid 1 part and brominated alkylphenol formaldehyde resin curing agent 10 parts were put into a Banbury mixer having a volume of 3 and kneaded at 200 ° C. and 50 rpm for 10 minutes to obtain a polyolefin elastomer (B-4).

Production of (B-5) The same masterbatch (m) used to produce (B-4)
235 parts, polypropylene 67 parts, zinc oxide 5 parts, stearic acid 1 part, and brominated alkylphenol formaldehyde resin curing agent 10 parts were kneaded under the same conditions as (B-4) to obtain a polyolefin elastomer (B-5). It was

Production of (B-6) The same masterbatch (m) used to produce (B-4)
235 parts, polypropylene 150 parts, zinc oxide 5 parts, stearic acid 1 part and brominated alkylphenol formaldehyde resin curing agent 10 parts are kneaded under the same conditions as (B-4) to obtain a polyolefin elastomer (B-6). It was

Production of (B-7) Master batch (m) identical to that used for production of (B-4)
235 parts, (B-6) 160 parts, zinc oxide 5 parts, stearic acid 1 part and brominated alkylphenol formaldehyde resin curing agent 10 parts were kneaded under the same conditions as in (B-4) to obtain a polyolefin-based elastomer (B -7) got.

Examples 1 to 13 Polyether ester amides (A-1), (A-2) and (A-3) mixed with the polyolefin-based elastomer shown in the table, 200
The mixture was melt-kneaded with an extruder having a diameter of 30 mm and heated to ℃, and then pelletized. The obtained pellets are molded at a temperature of 200 ° C and a mold temperature of 40 using an injection molding machine having an injection capacity of 5 ounces.
JIS No. 2 tensile test pieces and tear test pieces (thickness 2 mm) were molded at ℃. Shore hardness is ASTM D-2240, tensile strength is ASTM
D-638 and tear strength were measured according to JIS K6301.
The molding cycle was the holding pressure time + cooling time for obtaining a good JIS No. 2 tensile test piece. Further, the presence or absence of sink marks at the gate opening of the molded test piece was visually determined. The results are shown in the table.

Comparative Examples 1 to 10 polyether ester amide (A-1), (A-2) and (A-3),
Polyolefin elastomer (B-1), (B-2), (B-3), (B-
4), (B-5), (B-6) and (B-7) were molded into a JIS No. 2 tensile test piece and a tear test piece in the same manner as in Examples 1 to 13 to obtain Shore hardness, tensile strength and tear strength. The molding cycle was measured. Also, the presence or absence of sink marks on the molded piece was determined. The results are shown in the table.

The following can be seen from the results in the table.

As can be seen from Examples 1 to 13, the resin composition of the present invention has excellent tear strength, tensile strength, moldability and flexibility at the same time.

As seen in Comparative Examples 1 to 3, the polyether ester amide has a long molding cycle and has insufficient moldability.

As seen in Comparative Examples 4 to 10, the polyolefin-based elastomer had sink marks on the molded pieces, and had low tear strength and tensile strength.

<Effect of the Invention> In the present invention, a thermoplastic resin composition having excellent tear strength, tensile strength, moldability and flexibility at the same time can be obtained by blending a polyether-based ester amide with a polyolefin elastomer.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-58-125735 (JP, A) JP-A-58-15554 (JP, A) JP-A-51-28133 (JP, A) JP-A-49- 8472 (JP, A) US Patent 3044987 (US, A)

Claims (1)

[Claims] 1. A salt of an aminocarboxylic acid or lactam having 6 or more carbon atoms or a dicarboxylic acid having 6 or more carbon atoms (a), a poly (alkylene oxide) glycol (b) having a number average molecular weight of 300 to 6,000. ), And 1 to 99% by weight of a polyetheresteramide (A) derived from a dicarboxylic acid (c) having 4 to 20 carbon atoms.
In addition, a polyolefin-based elastomer (B) made of polypropylene and vulcanized ethylene-based copolymer rubber is added to 99-
A thermoplastic resin composition prepared by blending at a ratio of 1% by weight.