JPS6069159A - Production of polyamide composition - Google Patents

Abstract

PURPOSE:To form a polyamide compsn. having excellent impact resistance as well as improved chemical resistance and water absorption ratio, by melt-kneading a polyamide, a modified ethylene copolymer and an ethylene copolymer rubber. CONSTITUTION:A modified ethylene copolymer obtd. by melt-kneading 100pts.wt. ethylene copolymer (a) selected from an ethylene/unsaturated carboxylic ester copolymer (e.g. an ethylene/ethyl acrylate copolymer) and a copolymer composed of ethylene, an unsaturated carboxylic ester and a metal salt of an unsaturated carboxylic acid (e.g. an ethylene ionomer resin), 0.01-5pts.wt. peroxide (b) and 0.05-5pts.wt. unsaturated compd. (c) (e.g. maleic anhydride), is used. 40-99pts. wt. polyamide, 1-60pts.wt. said modified ethylene copolymer and 0-40pts.wt. ethylene copolymer rubber such as EPR are melt-kneaded together at 200-320 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a new method for producing a polyamide composition with excellent impact resistance.

Generally, polyamide has excellent abrasion resistance, electrical properties, heat resistance, mechanical strength, etc., and is widely used as an engineering resin for various mechanical parts materials, but it has the drawback of insufficient impact resistance.

Conventionally, various studies have been conducted on methods of improving the impact resistance of polyamide, and one of the methods proposed is a method of blending an ethylene copolymer with polyamide.

In a method for improving the impact resistance of polyamide using an ethylene copolymer.

The present invention was achieved as a result of intensive research aimed at developing a method that can further improve the impact resistance of paper sheets compared to known methods.

In other words, the present invention is as follows.

(a) 40 to 99 parts by weight of polyamide.

(t,) Consists of (1) a copolymer of ethylene and an unsaturated carboxylic acid ester, and (2) a monomer unit of ethylene, an unsaturated carboxylic acid, an unsaturated carboxylic acid ester, and an unsaturated carboxylic acid metal salt. 100 parts by weight of an ethylene copolymer selected from copolymers.

1 to 60 parts by weight of a modified ethylene copolymer obtained by melt-kneading 0.01 to 5.0 parts by weight of a peroxide and 0.05 to 5.0 parts by weight of an unsaturated compound;

(C) A new method for producing a polyamide composition having excellent impact resistance is provided by melt-kneading 0 to 40 parts by weight of ethylene copolymer rubber.

The polyamide composition obtained by the production method of the present invention is as follows.

It has extremely high impact resistance, maintains high impact resistance even at low temperatures, and has improved water absorption and chemical resistance.

Next, the present invention will be explained in detail.

Examples of polyamides used in the present invention include nylon 6, nylon 11. Polylactams such as nylon 12; nylon 66, nylon 610, nylon 61
Polyamides obtained from dicarboxylic acids such as 2 and diamine; nylon 6/66, nylon b/b1o, nylon 6/12°, nylon 6/612. Nylon 6/66/
610° Copolymerized polyamides such as nylon 6766/12; nylon 6/6T (T: terephthalic acid component), semi-polyamides obtained from aromatic dicarboxylic acids such as isophthalic acid and metaxylene diamine or alicyclic diamine. Aromatic polyamides; polyesteramide,
Mention may be made of polyetheramides and polyesteretheramides. Note that the polyamide may be used alone, or two or more types of polyamide may be used in combination.

As long as the polyamide that can be used in the present invention is selected from the above-mentioned polyamides, various polyamides can be used without being limited by the type, concentration, molecular weight, etc. of the terminal groups of these polyamides. It is also possible to use polyamide in which low molecular weight substances such as monomers and oligomers that remain or are generated during polymerization of polyamide are mixed.

Examples of copolymers of ethylene and unsaturated carboxylic acid esters used in the present invention include copolymers of ethylene and esters selected from the group of ethyl acrylate, methyl acrylate/ethyl methacrylate, and methyl methacrylate. Polymers may be mentioned. The content of ester units in the copolymer.

There are no particular restrictions on the melt index of the copolymer, but
A preferred copolymer is ethylene-ethyl acrylate copolymer.

Further, as the ethylene copolymer composed of monomer units of ethylene, unsaturated carboxylic acid, unsaturated carboxylic acid metal salt, and unsaturated carboxylic acid ester used in the present invention, ethylene ionomer resin can be mentioned.

Examples of unsaturated carboxylic acids include acrylic acid, methacrylic acid, and itaconic acid, and metal species of their metal salts include sodium, potassium, and magnesium.

Examples include barium and zinc.

Unsaturated carboxylic acid esters include ethyl acrylate, methyl acrylate, ethyl methacrylate, and methyl methacrylate.

The melt index of ethylene ionomer resin is
A value of 7.0 or less as measured by the method of ASTM-1238 is preferable. Also, what is its embrittlement temperature?

It is preferable that the temperature is -40°C or less as measured by the method of ASTM-D-746.

These ethylene-based ionomer resins can be of various grades commercially available under the name "Sohaimilan" (registered trademark manufactured by Nimitsui Polychemical Co., Ltd.).
Among them, Himilan 1706°1855.1554,
Grades such as 1650.1652 are preferred.

The peroxide used in the present invention is one that functions as a reaction initiation catalyst or a crosslinking agent. Examples thereof include tert-butyl hydroperoxide, di-tert-butyl peroxide, dicumyl peroxide, and penzoyl peroxide. These compounds are appropriately selected and used.

The amount of peroxide added is 0.01 to 5.0 parts by weight per 100 parts by weight of the ethylene copolymer, preferably [0
, 1 to 2.0 parts by weight. The amount of peroxide added is 0.80
If it is less than 1 part by weight, it will be difficult to function as a reaction initiator. Moreover, even if more than 5.0 parts by weight is added, there is no change in the reaction initiation effect.

Examples of unsaturated compounds used in the present invention are:

Examples include α, β unsaturated carboxylic acids, monoesters and anhydrides thereof, and the like. More specific examples include acrylic acid, methacrylic acid, maleic acid, maleic acid monomethyl ester, maleic anhydride, itaconic acid, itaconic acid monomethyl ester, itaconic anhydride, fumaric acid, derivatives thereof, and acids thereof. metal salts and the like. Also, alicyclic carboxylic acids, more specifically endo-bicyclo(2,2,1)-s-hebutene-2,3-carboxylic acid anhydride, cis-4-cyclohexene-1,2-carboxylic acid Anhydrous.

and derivatives thereof, metal salts of these acids, etc. can be used. Alternatively, epoxy group-containing compounds such as glycidyl methacrylate can also be used as unsaturated compounds in the present invention.

In the present invention, the preferred unsaturated compound is an acid anhydride, and the most suitable compound is maleic anhydride.

The amount of the unsaturated compound added is 0.05 to 5.0 parts by weight per 100 parts by weight of the ethylene copolymer.

Preferably it is 0.1 to 2.0 parts by weight. If the amount of the unsaturated compound added is less than 0.05 parts by weight, the resulting composition will have poor impact resistance, and if it is more than 5.0 parts by weight, the resulting composition will gel.

The modified ethylene copolymer in the present invention is usually obtained by adding a peroxide and an unsaturated compound to an ethylene copolymer and melt-kneading the mixture.

The temperature during melt-kneading is usually 200 to 350°C, preferably 220 to 350°C.

The ethylene copolymer rubber that may be used in the present invention is a copolymer of ethylene and an α-olefin having 3 or more carbon atoms, or a copolymer of these and a non-conjugated diene.

As the α-olefin having 5 or more carbon atoms, propylene,
Examples include butene-1 and hexene-1.

Specific examples of non-conjugated dienes include 1,4-hexadiene, pentadiene, dicyclopentadiene, and methyltetrahydroindene.

Examples include methylene norbornene and ethylidene norbornene.

In these ethylene-based copolymer rubbers, the content of ethylene units is preferably 50 to 90 mol, particularly preferably 50 to 85 mol, and the content of nonconjugated diene is 0.01 to 90 mol.
Preferably it is 10 moles, especially 0.1 to 5 moles.

The proportions of the polyamide, modified ethylene copolymer and ethylene copolymer rubber are 1 to 60 parts by weight of the modified ethylene copolymer and 0 to 40 parts by weight of the ethylene copolymer rubber to 40 to 99 parts by weight of the polyamide.

Preferably, the amount is 10 to 50 parts by weight of the modified ethylene copolymer and 0 to 25 parts by weight of the ethylene copolymer rubber to 90 to 50 parts by weight of the polyamide.

If the amount of the modified ethylene copolymer is less than the lower limit, it will not be possible to impart sufficient impact resistance to the resulting polyamide composition, and if it is larger, the tensile strength of the resulting polyamide composition will decrease171 The rate of decrease in heat distortion temperature increases.

In the present invention, it is preferable to use a modified ethylene copolymer and an ethylene copolymer rubber together in order to further improve the impact resistance of the resulting composition. The preferred amount of ethylene copolymer rubber used in combination is polyamide 9
The amount is 6 to 25 parts by weight relative to 0 to 50 parts by weight.

When producing a polyamide composition, the polyamide and the modified ethylene copolymer, as well as these and the ethylene copolymer rubber, can be melt mixed in various conditions. For example, other components may be added to the polyamide that is still in a molten state after the completion of the polymerization reaction and then melt-kneaded.
Alternatively, other components may be added to powdered or pelleted polyamide and mixed by melting.

The temperature when melting and kneading each component is usually 200 to 520.
℃, preferably selected from the range of 240 to 300℃.

If the melt mixing temperature is lower than 200°C, the melting of the raw materials will be insufficient and it will be difficult to completely melt and knead, and if it is 320°C or higher, a decomposition reaction will occur, which is not preferable.

The melt-kneading operation for producing the polyamide composition can be carried out using a known melt-mixing device such as a 6-twin screw extruder.

The polyamide composition obtained in the present invention may contain dyes, pigments, fillers, nucleating agents, and fibrous materials depending on the purpose.

Appropriate amounts of plasticizers, lubricants, blowing agents, heat resistant agents, weathering agents, flame retardants, etc. may be added. The polyamide composition obtained in the present invention can be processed into films, pipes, tubes, rods, blow molded products, injection molded products, etc.
After processing, it is plated.

It is also possible to perform processing such as painting. or.

It can also be used as an adhesive for manufacturing composite materials by laminating and bonding multiple metal plates.

Next, Examples and Comparative Examples of the present invention will be shown.

[Method of Creating a Test Piece] A test piece was created by molding the base nylon and the composition using a screw in-line injection molding machine. The cylinder temperature at this time is 250°C when nylon 6 is used as the polyamide, 280°C when nylon 66 is used, and Dynam as the amorphous aromatic polyamide.
Troga made by it Nobel A G (West Germany)
290°C for mid-T and 270°C for compositions using nylon 6 and 66*
In the case of compositions using Trogamid-T, 2
90°C, and the mold temperature was all 80°C.

[Test method for molded products]

1. Izot impact test (with notch) AEIT on two types of test pieces of 1/2 inch and 1/8 inch width
An Izot impact test (notched) was carried out at 23° C. according to the provisions of M-D-256. Measurements are in units of rim/cm
/an is displayed.

The compatibility of the composition after two-compatibility melt intermixing was evaluated by a strand bending test.

The raw materials used in the Examples and Comparative Examples are shown below.6 Polyamide relative viscosity (J-K-6810): Ijr Nylon 6 (1) (manufactured by Ube Industries, Ltd.) [ηr” 2.80
+Amino end group concentration=8.50X10-' eq/7
, carboxyl end group concentration = 1.70 X 10-'θ
q/7) ・Nylon 6 (2) (manufactured by Ube Industries ■) [ηr=”s,
17 + amino end group concentration = 2.85X10''''5θ
q/? - Carboxyl end group concentration = 5.26 x 10
-'+3q/7)・Nylon 66 (manufactured by Ube Industries) [ηr''= 2.95 r amino end group concentration= 5.7
9 Xl 0 ''eq/f, carboxyl end group concentration = 6, S 9 Combined ■Ethylene-ethyl acrylate copolymer (umA) (manufactured by Nippon Unicar) ・mmA (1)...DPD, T-6169 ester content = 18% by weight Melt index (A8TM D 1238°190
°C, 2160 t)=6 (f/10m1n)-E
l! 1A(2)...DPDJ-8026 ester content = 8% by weight Melt index = 13 (f/10m1n)
, HBA (8)...NUO-6220 ester content = 7% by weight Melt index = 4 (f/10m1n) ■ Ethylene ionomer resin (Ko R) (manufactured by Mikata Polychemical ■) O Ko R (1 ) Himilan 1706 / Engineering R (2) Hi ξlan 1855 Ethylene copolymer rubber (manufactured by Japan Synthetic Rubber) O ethylene propylene copolymer elastomer (mpR)
]! 1p-02F O ethylene-propylene-ethylidene norbornene copolymer rubber (FjPDM) BP-57P peroxide (manufactured by NOF ■) ・Niper B (benzoyl peroxide) ・Perbutyl U (t-butyl hydroperoxide) Unsaturated compound/Unsaturated compound (1) Maleic anhydride (MAR)/Unsaturated compound (2) Endo-bicyclo(2,2,1) -5-hebutene-2
, 6 carboxylic acid anhydride Example 1 a) Production of modified ethylene copolymer 100 parts by weight of EEA (1) and unsaturated compound (1) [30.5 parts by weight of maleic anhydride and peroxide (Perbutyl H) 0 .3 parts by weight were blended in a tumbler type mixer, melted and kneaded using a twin-screw extruder at 220°C, screw rotation speed 40 rpm + discharge rate 2Kg/hr, pelletized, and then 50°C. Modified EEA grafted with maleic anhydride by drying under reduced pressure for 48 hours
A beret of (1) was obtained.

b) Production and injection molding of polyamide compositions, measurement of Izot impact strength Modified E1 prepared with 65 parts by weight of nylon 6(1) and a)
After tri-blending with 35 parts by weight of 1iA(1).

Using a twin-screw pushing machine, 250℃, Scree rotation speed 110
Melt and knead under the conditions of 0 rpm + discharge rate aKg/hr.

After pelletizing, the resulting pellets were dried under reduced pressure at 80° C. for 48 hours.

This pellet was then injection molded and its Izod impact strength was measured.

Example 2 a) Production of modified ethylene copolymer 10 parts by weight of mEA (1), 0.5 parts by weight of maleic anhydride and 16 parts by weight of Tipper 3 were blended in a tumbler type mixer, and then a twin-screw extruder was used. After melt-kneading and pelletizing under the conditions of 220°C, screw rotation speed 40 rpm, and discharge rate 2 Kg/hr, the modified E1!1A (maleic anhydride-grafted) A beret of 1) was obtained.

b) Manufacture and injection molding of polyamide composition, measurement of Izot impact strength Modified ll produced with 65 parts by weight of nylon 6(1) and a)
111! ! The same experiment as in b) of Example 1 was conducted except that 29 parts by weight of A(1) and 6 parts by weight of ethylene copolymer rubber (gP-02P') were used.

Example 3 Bmi(1) in a) of Example 1 is F! ]! ! A (
The same experiment as in Example 1 was conducted except that 2) was replaced.

Example 4 ERA (1) of Example 2 a) le K A (2)
An experiment similar to Example 2 was conducted except that .

Example 5 The same experiment as in Example 2 was conducted except that mBA (1) in a) of Example 2 was changed to EFiA (2) and Nyvar-B was changed to Perbutyl H.

Example 6 mmA(i) of Example 2 a) was replaced with IEA (2), Nybar B was replaced with Perbutyl H, and 29 parts by weight of modified E11iA (1) of Example 2 b) was replaced with modified ERA ( 2)2
1 part by weight.

6 parts by weight of ethylene copolymer rubber (IP-02F) to 14
The same experiment as in Example 2 was conducted except that parts by weight were changed.

Example 7 Fi E A (2) of gEA (1) in a) of Example 2
and Niper B to Perbutyl H, and b) of Example 2.
The same experiment as in Example 2 was conducted except that nylon 6(1) was replaced with nylon 6(2).

Example 8 imA(1) in a) of Example 2 is 1! ! In EA (2),
The same experiment as in Example 2 was conducted, except that Nybar B was replaced with Perbutyl H, nylon 6(1) in b) of Example 2 was replaced with nylon 66, and the temperature of the twin-screw extruder was raised to 280C. .

Example 9 ll1EA(1) in a) of Example 1 is v E A (8
) was replaced with the same experiment as in Example 1 except that

Example 10 The same experiment as in Example 2 was conducted except that ggA (1) in a) of Example 2 was replaced with KEA (8) and Niper-B was replaced with Perbutyl H.

Example 11 Ili in a) of Example 1]! ! A (1) as KFi
A(2), Nyper B to Perbutyl H, and 65 parts by weight of nylon 6(1) in b) of Example 2 to Trogam.
The same experiment as in Example 1 was carried out, except that 80 parts by weight of id-T and 55 parts by weight of modified PEA (1) were replaced with 80 parts by weight of modified ERA (2), and the temperature of the twin-screw extruder was raised to 290°C. Ta.

Example 12 m1A(t) in a) of Example 2 is K 118 A (2
), Niper B to Perbutyl H, unsaturated compound (1
) was replaced with unsaturated compound (2), but the same experiment as in Example 2 was conducted.

Example 13 a) Production of modified ethylene copolymer 100 parts by weight of IR (1), 0.5 parts by weight of maleic anhydride and 3 parts by weight of perbutyl HO00 were blended in a tumbler type mixer, and then blended using a twin-screw extruder. After melt-kneading and pelletizing at 220°C, screw rotation speed 40 rpm, and discharge rate 2/br, the modified product R (1
) obtained a beret.

b) Manufacture and injection molding of polyamide composition, measurement of Izot impact strength Modified material R manufactured with 65 parts by weight of nylon 6(1) and a)
(1) After tri-blending 35 parts by weight, using a twin-screw extruder, 250° C. and screw rotation speed io.

After melt-kneading and pelletizing under the conditions of rpm and discharge rate of 4 kg/hr, the obtained pellets were dried under reduced pressure at 80° C. for 48 hours.

Next, the Izot impact strength of the untreated molded product obtained by injection molding using this pellet and the heat-treated molded product was measured.

The method for measuring the Izot impact strength of the heat-treated molded product is as follows.

Heat treatment (heat resistance): 1 piece of notched Izotsu impact test piece
The sample was placed in a gear opener at 50°C, taken out after 50 days, cooled in a desiccator, and measured at 26°C.

Example 14 The blending composition in b) of Example 13 was changed to nylon 6(1).
Example 1 except that 65 parts by weight, 29 parts by weight of modified R (1), and 6 parts by weight of ethylene copolymer rubber (KP-02F)
An experiment similar to 5 was conducted.

Example 15 The same experiment as in Example 15 was conducted except that in a) of Example 13, Engineering R(1) was replaced with Engineering R(2) and Niper B, which was perbutyl H, was used.

Example 16 The composition in b) of Example 16 was changed to 65 parts by weight of nylon 6(1) by replacing the process R(1) in a) of Example 15 with process R(2) and the perbutyl H Niper B. Modification R (2
) 29 parts by weight, ethylene copolymer rubber (HP-02P)
The same experiment as in Example 13 was conducted except that the amount was changed to 6 parts by weight.

Example 17 The composition R(1) in a) of Example 15 was changed to 1R(2), and the blending composition in b) of Example 1 was 65 parts by weight of nylon 6(1).

29 parts by weight of modified R (2), ethylene copolymer rubber (u
p-57F) The same experiment as in Example 16 was conducted except that the amount was 6 parts by weight.

Comparative Examples 1 to 4 Nylon 6 (1), Nylon 6 (2), Nylon 66 and Trogamid-T were each injection molded and their Izot impact strength was measured.

Comparative Example 5 65 parts by weight of nylon 6(1) and 3s parts by weight of ethylene ethyl acrylate mmn(1) were triblended, and the resulting mixture was heated at 250°C using a twin-screw extruder with a screw diameter of 30. Melt kneading was carried out under the conditions of a screw rotation speed of 20 rpm and a discharge rate of 4 kg/hr.

After pelletizing, the resulting pellets were dried under reduced pressure at 80° C. for 48 hours.

This pellet was then injection molded and its Izod impact strength was measured.

Comparative Example 6 65 parts by weight of nylon 6(1) and III! EA(1)29
Weight parts and ethylene copolymer rubber (EP-02F) 6
An experiment was conducted in the same manner as in Comparative Example 5 except that parts by weight were used.

Comparative Example 7 An experiment similar to Comparative Example 5 was conducted except that E K A (1) in Comparative Example 5 was replaced with I m A (2).

Comparative Example 8 An experiment similar to Comparative Example 6 was conducted except that PEA (1) in Comparative Example 6 was replaced with ]IJcA (2).

Comparative Example 9 An experiment similar to Comparative Example 5 was conducted except that EEA (1) in Comparative Example 5 was replaced with EEA (8).

Comparative Example 10 E K A (1) of Comparative Example 6 is 1! ! llim (8)
An experiment similar to Comparative Example 6 was conducted except that .

Comparative Example 11 65 parts by weight of nylon 6(1) and 35 parts by weight of Engineering R(1) were triblended, and the resulting mixture was heated at 250°C and at a screw rotation speed using a twin-screw extruder with a screw diameter of 50111 m. After melt-kneading and pelletizing under the conditions of 200 rpm and a discharge rate of 4 Kf/hr, the obtained pellets were
It was dried under reduced pressure at ℃ for 48 hours.

Next, the Izot impact strength of the untreated molded product obtained by injection molding using this pellet and the heat-treated molded product was measured.

In addition, the Izot impact of the heat-treated molded product is 150
The sample was placed in a gear opener at 23°C, taken out after 50 days, cooled in a desiccator, and measured at 23°C.

Comparative Example 12 The same experiment as Comparative Example 11 was conducted except that 65 parts by weight of nylon 6(1), 29 parts by weight of Engineering R(1) and 6 parts by weight of ethylene copolymer rubber (IP-02F) were used. .

Comparative Example 15 The same experiment as in Comparative Example 11 was conducted except that R(1) in Comparative Example 11 was replaced with R(2).

Comparative Example 14 The same experiment as in Comparative Example 12 was conducted except that R(1) in Comparative Example 12 was replaced with R(2).

Comparative Example 15 Process R (1) of Comparative Example 12 was replaced with Process R (2), and the ethylene copolymer rubber (BP-02P) was replaced with the ethylene-propylene-ditylidene norbornene copolymer rubber (EP-5'7 F
) was replaced, but the same experiment as Comparative Example 12 was conducted.

The results of each of the above Examples and Comparative Examples are shown in Tables 1 and 2.

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Claims (1)

[Scope of Claims] (a) 40 to 99 parts by weight of polyamide, (b) (1) a copolymer of ethylene and an unsaturated carboxylic acid ester, and. (2) 100 parts by weight of an ethylene copolymer selected from copolymers consisting of monomer units of ethylene, unsaturated carboxylic acids, unsaturated carboxylic acid esters, and unsaturated carboxylic acid metal salts. 0.01-5.0 parts by weight of peroxide and 0 unsaturated compounds
．． 1 to 60 parts by weight of a modified ethylene copolymer obtained by melt-kneading 05 to 5.0 parts by weight, and (0) A method for producing a polyamide composition, which comprises melt-kneading 0 to 40 parts by weight of an ethylene copolymer rubber.