JPS63238161A - Rubbery resin composition - Google Patents

Abstract

PURPOSE:To obtain a rubbery resin composition having excellent moldability and improved oil resistance, weather resistance and ultraviolet light resistance, by compounding a polyamide resin with a crosslinked polyoctenylene rubber, a crosslinked EPDM and an alpha,beta-unsaturated carboxylic acid (derivative). CONSTITUTION:(A) A polyamide resin (e.g. polyether amide) is kneaded with (B) a polyoctenylene rubber preferably having a trans-content of 52-90% and a crystallinity of 5-70%, (C) an EPDM rubber and (D) an alpha,beta-unsaturated carboxylic acid (derivative) under a condition to effect the melting of the component A, and melt crosslinking of the components B and C and the reaction of the component D. Preferably, the components B and/or C are uniformly mixed with a crosslinking agent (e.g. a peroxide or sulfur) and/or a crosslinking accelerator at a low temperature (<=100 deg.C) and the mixture is kneaded with the components A and D at 150-270 deg.C e.g. in nitrogen atmosphere in a state shielded from air.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a rubber-like resin composition, and more specifically, it is made by mixing a polyamide resin and two specific types of rubber in a specific state. A composition that can be easily molded in the same manner as a thermoplastic resin, has rubber-like elasticity, and has improved some of the drawbacks of rubber, and a method for producing the same.
It is something.

(Prior Art and Problems) Rubber is used in a wide range of fields due to its excellent elasticity and flexibility. However, in order to impart these properties to rubber, an intermolecular crosslinking process, commonly referred to as vulcanization, is required, and this is one of the major reasons for the poor moldability of rubber. .

In an attempt to improve this moldability, by mixing rubber and thermoplastic resin, the desired shape can be formed by simply applying heat to make it flow, then cooling and solidifying it, just like normal thermoplastic resin. Many proposals have been made to obtain processable rubbery compositions.

For example, Japanese Patent Publication No. 55-14096 proposes an elastoplastic composition composed of polyamide and crosslinked butadiene polymer, but this composition has poor weather resistance and ultraviolet resistance due to the butadiene polymer. However, it has the disadvantage that its applications are limited.

Furthermore, JP-A-57-5753 discloses a composition made of polyamide and hardened epichlorohydrin rubber, but it does not have sufficient flexibility.

In addition, JP-A-59-49246 discloses a composition in which a polyamide, a specific nitrile rubber, and a curing agent are mixed.
JP-A-60-96631 proposes a composition in which a polyamide, a specific nitrile rubber, a specific epichlorohydrin rubber, and a curing agent are mixed, but the dispersibility of the rubber is poor, and the flexibility and elasticity are poor. Similarly, it is not sufficient.

As a result of intensive research to solve these drawbacks, the present inventors have blended polyamide resin with crosslinked polyoctenylene rubber and crosslinked EPDM, and further added α,β-unsaturated carboxylic acid or its derivative. It has been found that the rubber-like resin composition blended with the present invention is easy to mold, improves the drawbacks of rubber in terms of oil resistance, weather resistance, ultraviolet resistance, etc., and has sufficient flexibility and elasticity. Further, such a composition can be easily obtained by kneading under conditions in which the polyamide resin is melted, the polyoctenylene rubber and EPDM are melt-crosslinked together, and the α,β-unsaturated carboxylic acid or its derivative reacts. This discovery led to the completion of the present invention.

(Means for Solving the Problems) That is, the present invention blends crosslinked polyoctenylene rubber and crosslinked EPDM into a polyamide resin, and further includes α,
It is a rubbery resin composition containing β-unsaturated carboxylic acid or its derivative. Further, when blending polyoctenylene rubber, EPDM, and α,β-unsaturated carboxylic acid or its derivative into polyamide resin, the polyamide resin melts, the polyoctenylene rubber and EPDM melt and crosslink, and the α, A method for producing a rubbery resin composition, comprising a step of kneading under conditions in which a β-unsaturated carboxylic acid or a derivative thereof reacts.

The polyamide resin in the present invention includes caprolactam,
Lactams such as lauryllactam, ω-aminocarboxylic acids such as 12-aminododecanoic acid and 11-aminoundecanoic acid, dicarboxylic acids such as adipic acid and hexamethylene diamine, dodecanoic acid and hexamethylene diamine, isophthalic acid and isophorone diamine, etc. Examples include resins obtained by condensation polymerization of and diamine.

In addition, this polyamide resin is obtained by condensation polymerization of 21 or more lactams such as caprolactam and lauryllactam or hexamethylene diamine, dodecanedioic acid and isophthalic acid, ω-aminocarboxylic acid, diamine and dicarboxylic acid. Naturally, it also includes copolymerized nylon, and those called polyetheramide, polyesteramide, or polyetheresteramide whose main components are lauryllactam and tetramethylene glycol.

The polyoctenylene rubber used in the present invention is obtained by forming butadiene into two sets and then metathesizing octenylene, which is a cyclic compound with one double bond remaining by hydrogenation. Among them, the trans content is 52~
90%, and those having a crystallinity in the range of 5 to 70% are preferably used.

The EPDM used in the present invention is a general synthetic rubber obtained by copolymerizing ethylene, propylene, and dienes, and various commercially available EPDMs can be used.

Examples of the α,β-unsaturated carboxylic acid or its derivative used in the present invention include monocarboxylic acids such as acrylic acid and methacrylic acid, oleic acid, fumaric acid, and acid anhydrides thereof.

Dyes and pigments, various stabilizers, fillers, plasticizers, oils, etc. can be added to the polyamide resin in the present invention.

In addition, the polyoctenylene rubber and butyl rubber used in the present invention include fillers such as carbon black, zinc white, magnesium oxide, stearic acid, and silica, oils such as extender oil, various stabilizers such as anti-aging agents, and lubricants. can be added.

The rubbery resin composition of the present invention is produced by kneading under conditions in which the polyamide resin melts, the polyoctenylene rubber and EPDM crosslink while melting, and the α,β-unsaturated carboxylic acid or its derivative reacts. can get. In this case, polyoctenylene rubber and EPDM can be self-crosslinked by heat, but it is preferable to heat them as a homogeneous mixture with a crosslinking agent or a crosslinking accelerator. Examples of crosslinking agents include peroxide, sulfur, organic sulfide, bismaleimide, and epoxy compounds, and examples of crosslinking accelerators include thiazole, thiuram, and
Examples include guanidine compounds. The heating temperature is 150 to 27 from the viewpoint of ease of crosslinking, crosslinking reaction rate, and prevention of deterioration.
0°C is preferred.

In addition, in order to carry out the crosslinking reaction efficiently, a crosslinking agent and/or a crosslinking accelerator, etc. are uniformly mixed in advance with the polyoctenylene rubber and/or EPDM at a low temperature of 100°C or less, and then the polyamide resin and α , β-unsaturated carboxylic acid or its derivative to complete the crosslinking reaction.

In the present invention, the mixing of the polyamide resin, polyoctenylene rubber, EPDM, and α,β-unsaturated carboxylic acid or its derivative is done in a kneader such as a Banbury mixer, a roll, an extruder, etc., but the oxidation of the resin and rubber is In order to prevent deterioration, it is more preferable to knead in a state where air is blocked, such as in a nitrogen atmosphere.

The method for obtaining the composition of the present invention is characterized in that polyoctenylene rubber, EPDM, and α,β-unsaturated carboxylic acid or its derivative are kneaded while crosslinking and reacting. Crosslinking should be continued until crosslinking is almost complete; if crosslinking is stopped before crosslinking has progressed, moldability will be difficult due to poor dispersion, and flexibility and elasticity may be developed due to insufficient crosslinking. I won't be able to do it.

(Effects of the Invention) The rubber-like resin composition obtained in the present invention is flexible and highly elastic, has excellent gasoline resistance, chemical resistance, ozone resistance, weather resistance, ultraviolet resistance, etc. Like thermoplastic resins, it can be easily molded, so it is used, for example, by extrusion molding into a tube, as a coating on a wire, or into a flexible sheet. Furthermore, it can be easily molded into shoes, clips, etc. by injection molding, compression molding, etc., and can also be molded into diaphragms, bellows, etc. by blow molding.

(Example) The present invention will be explained in further detail by giving examples below.

Examples 1 to 5 Nylon 12 (Diamid L1940 manufactured by Daicel-Hüls), polyoctenylene comb (VESTENAHER 8012 manufactured by Huls), EPDM in the proportions shown in Table 1
(JSREP manufactured by Japan Synthetic Rubber Co., Ltd.) and maleic anhydride, 2 parts of metaphenylene bismaleimide, 0.2 parts of lauroyl peroxide, 5 parts of zinc oxide, stearin per 100 parts by weight of the rubber. Lol!
i2 parts by weight were charged at once into a Henschel mixer, tri-blended and mixed with Toshiba 55aw + twin-screw extruder.
After extrusion at 20°C, it was made into pellets using a pelletizer. The pellets were molded into bend test pieces and isot test pieces using a conventional injection molding machine. When the flexural modulus and Izot impact strength of these test pieces were determined, they were found to have good appearance and physical properties. Furthermore, using these bending test pieces, in an atmosphere of 40°C and 50 ppm of ozone, a cycle of 0 to 30 rpm between 60 # of chucks
Dynamic elongation was performed with a stroke of 5 m, the time until the sample broke was measured, and this value was taken as the ozone resistance value.

These results are shown in Table 1.

Example 6 Nylon 6 (Amiran CM10 manufactured by Toshi) in the proportions shown in Table 1
21) Polyoctenylene rubber, EPDM, and maleic anhydride, and 5 to 8 parts of metaphenylene bismaleimide and 0.5 parts by weight of benzothiazole disulfide per 100 parts by weight of the rubber were mixed at 250°C. The wire was inserted into a rheocord manufactured by HAAKE, which was set at Do you use the torque meter that comes with Leocord? I! As I noticed this, the torque increased little by little after the start of kneading, reaching 5 to 1
The maximum value was reached at 0 minutes. After this torque reaches its maximum,
Mixing was continued for about 8 minutes to allow sufficient crosslinking reaction, and then the contents were taken out. When this reactant is press-molded,
Sheets could be easily molded like thermoplastic resins. Bending test pieces and Izot test pieces were punched out from this sheet and the bending elastic modulus and Izot test piece strength were determined, and it was found that they exhibited good physical properties. Ozone resistance was also measured using these bending test pieces. The results are shown in Table 1.

Experimental Examples 7 to 9 Polyoctenylene rubber and EPDM in the proportions shown in Table 1,
A total of 10'0fiffi parts of the rubber was triblended with 2 parts by weight of metaphenylene bismaleimide, 0.3 parts by weight of lauroyl peroxide, 5 parts by weight of zinc oxide, and 2 parts by weight of stearic acid in a Henschel mixer. After that, it was heated to 60℃ in a 30# shaft extruder made by Chuo Kikai.
The mixture was kneaded using a pelletizer and made into pellets using a pelletizer. This pellet was made of polyamide resin (nylon 612
;Diamid 01800, polyamide elastomer m manufactured by Daicel-Hüls;Diamid P manufactured by Daicel-Hüls
AEE40, nylon 12) and maleic anhydride were mixed together, kneaded at 220°C using a 55s two-wheel extruder, and after the crosslinking reaction was sufficiently carried out, pelletization was performed using a pelletizer. The pellets were molded into bend test pieces and isot test pieces using a conventional injection molding machine. Using these test pieces, the flexural modulus, Izot impact strength, and ozone resistance were determined. The results are shown in Table 1.

Comparative Examples 1 to 3 Bending test pieces and Izot test pieces were molded using an injection molding machine using the three types of rubber shown in Table 1.

Using these test pieces, the flexural modulus, Izot impact strength, and ozone resistance were determined. The results are shown in Table 1. It has become clear that polyoctenylene rubber has poor ozone resistance, and EPDM has poor moldability.

Comparative Examples 4 to 7 In Examples 1 to 5, using rubber in the proportions shown in Table 1,
The wires were mixed and molded in exactly the same manner as in Examples 1 to 5, and the flexural modulus, Izot impact strength, and ozone resistance were determined. The results are shown in Table 1. It has become clear that all of these rubbers have poor ozone resistance.

(Margin below)

Claims (1)

[Scope of Claims] 1. A rubbery resin composition in which a polyamide resin is blended with crosslinked polyoctenylene rubber and crosslinked EPDM, and further blended with an α,β-unsaturated carboxylic acid or a derivative thereof. 2. Polyoctenylene rubber and EPDM on polyamide resin
When blending the α,β-unsaturated carboxylic acid or its derivative, the polyamide resin melts, the polyoctenylene rubber and the EPDM melt crosslink, and the α,β-unsaturated carboxylic acid or its derivative 1. A method for producing a rubbery resin composition, comprising a step of kneading under reaction conditions.