JPS63145364A - Rubber-like resin composition - Google Patents

Abstract

PURPOSE:To provide the title compsn. having excellent flexibility, elasticity, moldability, resistance to weather and ozone, etc., by melt-kneading a polyamide resin with polyoctenylene rubber, nitrile/butadiene rubber and an alpha,beta-unsaturated carboxylic acid (derivative). CONSTITUTION:A polyamide resin (A) such as caprolactam, nylon 12, etc. is blended with polyoctenylene rubber (B) having a trans unit content of pref. 52-90% and a crystallinity index of 5-70%, nitrile/butadiene rubber (C) having a bonded nitrile content of pref. 10-50wt.%, an alpha,beta-unsaturated carboxylic acid (derivative) (D) (e.g., maleic acid or anhydride) and optionally, a crosslinking agent (E) such as bismaleimide, peroxide, etc. and a crosslinking accelerator (F) such as thiazole. The mixture is dry-blended in a Henschel mixer, etc. and melt-kneaded in a twin-screw extruder to crosslink the components B and C and to react the component D, thus obtaining the title compsn.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a rubbery resin composition, and more particularly, it relates to a rubber-like resin composition, and more particularly, a composition comprising a specific thermoplastic resin, two specific rubbers, and an α-unsaturated unsaturated carboxylic acid or its A rubber-like resin that is made by mixing derivatives in a specific state, can be easily molded in the same manner as ordinary thermoplastic resins, has rubber-like elasticity, and has improved some of the drawbacks of rubber. The present invention relates to a composition and a method for producing the same.

(Prior Art and Problems) Rubber is used in a wide range of fields due to its excellent elasticity and flexibility. However, imparting these properties to rubber requires an intermolecular crosslinking process generally called vulcanization, which is one of the major causes of poor moldability of rubber.

In an attempt to improve this moldability, by mixing rubber and thermoplastic resin, it can be processed into the desired shape 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 rubbery compositions that can be used.

For example, Japanese Patent Publication No. 55-14096 proposes an Elasto-Alastics 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 had the disadvantage that its uses were limited.

Further, JP-A-57-5753 proposes a composition comprising polyamide and hardened epichlorohydrin rubber, but the composition was not satisfactory in terms of flexibility.

In addition, JP-A-59-49246 discloses a composition in which polyamide, a specific nitrile rubber, and a curing agent are mixed, and JP-A-59-168056, JP-A-60-96630, JP-A-60-96631, etc. Compositions in which polyamide, a specific nitrile rubber, a specific epichlorohydrin, and a curing agent are mixed have been proposed, but the dispersibility of the rubber is poor;
Moreover, it was insufficient in both flexibility and elasticity.

As a result of intensive research to solve these technical problems, the present inventors have developed a combination of polyamide resin, crosslinked polyoctenylene rubber, crosslinked nitrile butadiene rubber, and α-unsaturated unsaturated carboxylic acid or its derivatives. The composition is easy to mold, improves the disadvantages of rubber such as gasoline resistance, chemical resistance, weather resistance, ozone resistance, and ultraviolet resistance, and has sufficient flexibility and elasticity. I found it. Furthermore, this rubbery resin composition can be easily obtained by melting and kneading polyoctenylene rubber, nitrile butadiene rubber, and α-unsaturated carboxylic acid or its derivative in polyamide resin under specific conditions. The present invention has been completed based on these findings.

(Means for Solving the Problems) That is, the present invention blends a crosslinked polyoctenylene rubber and a crosslinked nitrile butadiene rubber with a polyamide resin, and further blends an α-unsaturated unsaturated carboxylic acid or a derivative thereof. It is a rubbery resin composition.

In addition, when blending polyoctenylene rubber, nitrile butadiene rubber, and α-unsaturated unsaturated carboxylic acid or its derivative into polyamide resin, the polyamide resin melts, the rubber melts and crosslinks, and the α-unsaturated unsaturated This is a method for producing a rubbery resin composition, which includes a step of kneading a carboxylic acid or a derivative thereof under conditions in which a carboxylic acid or a derivative thereof melts and 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 diamine and the like. In addition, this polyamide resin contains condensation polymerization of two or more lactams such as caprolactam, e-acryllactam, hexamethylene diamine, dodecanedioic acid, and isophthalic acid, ω-aminocarboxylic acid, diamine, and dicarboxylic acid. It goes without saying that the resulting copolymerized nylons and those called polyetheramides, polyesteramides, or polyetheresteramides whose main components are lauryllactam, tetramethylene glycol, etc. are also included.

The polyoctenylene rubber used in the present invention is obtained by dihydrogenating butadiene and then metathesizing octenylene, 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.

Furthermore, the nitrile butadiene rubber used in the present invention is
It is obtained by copolymerizing acrylonitrile and butadiene, and among them, those having a bound nitrile content in the range of 10 to 50% by weight are preferably used.

Furthermore, the α-unsaturated carboxylic acids or derivatives thereof used in the present invention include acrylic acid, methacrylic acid,
Examples include monocarboxylic acids such as oleic acid, dicarboxylic acids such as maleic acid and fumaric acid, and anhydrides thereof.

Dyes and pigments, various stabilizers, fillers, plasticizers, oils, etc. can be added to the polyamide resin in a3 of the present invention. In addition, the polyoctenylene rubber and nitrile butadiene rubber used in the present invention contain fillers such as carbon black, zinc white, magnesium oxide, stearic acid, and silica, oils such as extender oil, and various stabilizers such as anti-aging agents. , lubricants, etc. can be added.

The rubbery resin composition in the present invention is kneaded under conditions in which the polyamide resin is melted, the polyoctenylene rubber and nitrile butadiene rubber are melt-crosslinked, and the α-unsaturated, β-carboxylic acid or its derivative is melt-reacted. It can be obtained by In this case, polyoctenylene rubber and nitrile butadiene rubber 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 the crosslinking agent include peroxide, sulfur, organic sulfide, bismaleimide, and epoxy compounds, and examples of the crosslinking accelerator include thiazole, thiuram, and guanidine compounds. In terms of ease of crosslinking, crosslinking reaction rate, and prevention of deterioration, the heating temperature is preferably 150 to 270°C.

In order to carry out the crosslinking reaction efficiently, a crosslinking agent or/and a crosslinking accelerator or the like is added to the polyoctenylene rubber or/and nitrile butadiene rubber and the α-unsaturated unsaturated carboxylic acid or its derivative in advance.
It is also possible to homogeneously mix the mixture at a low temperature below C or lower, and then melt-mix it with the polyamide resin to complete the crosslinking reaction.

The mixing of the polyamide resin, polyoctenylene rubber, nitrile butadiene rubber, and α-unsaturated carboxylic acid or its derivative in the present invention is carried out using a roll, an extruder, etc., but the oxidative deterioration of the polyamide resin and the rubber is In order to prevent this, 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 invention comprises polyoctenylene rubber, nitrile butadiene rubber and α.

It is characterized by kneading while crosslinking and reacting the β-unsaturated carboxylic acid or its derivative, and preferably the kneading should be continued until the crosslinking of the rubber and the reaction of the compound are almost completed. If crosslinking is stopped before the crosslinking and reaction has barely progressed, moldability will be difficult due to poor dispersibility, and at the same time, flexibility and flexibility will be reduced due to insufficient crosslinking and reaction.
The expression of elasticity is no longer observed.

(Effects of the Invention) The rubber-like resin composition obtained by the present invention is flexible and highly elastic, has excellent gasoline resistance, chemical resistance, ozone resistance, weather resistance, ultraviolet resistance, etc., and has excellent resistance to ordinary heat. Since it can be easily molded like a plastic resin, it is used, for example, by extrusion molding into a tube shape, 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, or the like. Alternatively, it can be formed into a diaphragm, bellows, etc. by blow molding.

(Example) The present invention will be explained in detail with reference to Examples below.

Examples 1 to 5 Nylon 12 (Diamid L1940, manufactured by Daicel-Hüls), polyoctenylene rubber (VESTENAHE II 8012, manufactured by Huls), and nitrile-butadiene rubber (I N-22111, manufactured by JSR) in the proportions shown in Table 1.
and maleic anhydride, 2 parts by weight of metaphenylene bismaleimide per total blend ω of the rubber, and 0.21ffi
Part of the lauroyl peroxide was charged at once into a Henschel mixer and tri-blended, then kneaded in a 55 m twin-screw extruder at 220°C while causing a crosslinking reaction, and pelletized using a pelletizer.

Using this pellet, a tensile dumbbell piece and a bending test piece were molded using an ordinary injection molding machine, and the tensile strength and elongation and bending elastic modulus were measured. The results are shown in Table 1, and both the appearance and moldability were good.

Next, using this test piece, in an atmosphere of 40 ° C. and 50 ppm of ozone, dynamic stretching was performed with a stroke of 0 to 5 M at a cycle of 30 rpm with a chuck interval of 60 M, and the time until the sample broke was measured. This value was defined as ozone resistance. These results are shown in Table 1.

Example 6 Nylon 6 (Amiran CM1021), polyoctenylene rubber, nitrile butadiene rubber, and maleic anhydride in the proportions shown in Table 1, and 2% per total compounding amount of the rubber.
Metaphenylene bismaleimide from Jubobe and 0.5 parts by weight of benzothiazole disulfide were charged into a HAAKE rheocord set at 250°C, and the rotor rotation speed of the rheocord was set at 50 rpm. : Setting and kneading were performed. Observing the torque meter attached to the Rheocord, the torque increased little by little after the start of kneading and reached a maximum value in 5 to 10 minutes. After reaching this maximum torque, cross-talk was continued for about 8 minutes to sufficiently cause the crosslinking reaction, and then the contents were taken out. When this reaction product was press-molded, a sheet could be easily formed like a thermoplastic resin. Tensile dumbbell pieces and bending test pieces were made from this sheet, and the tensile strength and elongation, bending elastic modulus, and ozone resistance were investigated. Table 1 shows the results.
Shown below.

Examples 7 to 9 The total composition of polyoctenylene rubber, nitrile butadiene rubber, maleic anhydride and the rubber in the proportions shown in Table 1 was 2 parts by weight of metaphenylene bismaleimide and 0.3 parts by weight of lauroyl peroxide. side, 5 parts by weight of zinc oxide;
6 in a 30M twin screw extruder with 2 parts by weight of stearic acid.
After kneading at 0°C, the mixture was pelletized using a pelletizer.

This pellet was combined with polyamide resin (nylon 612; Daicel-Hüls Co., Ltd.'s Diaamide D18) as shown in Table 1.
00, polyamide elastomer m: Diamid PAE E40° Nylon 12) manufactured by Daicel-Hüls was melt-kneaded in a 55 tea 2 @extruder while causing a crosslinking reaction at 220°C, and pelletized using a pelletizer. Using this pellet, a tensile dumbbell piece and a bending test piece were molded using an ordinary injection molding machine, and the tensile strength and elongation, bending elastic modulus, and ozone resistance were measured. The results are shown in Table 1.

Comparative Examples 1 to 3 Using the three types of rubber shown in Table 1, tensile dumbbell pieces and bending test pieces were molded using an ordinary injection molding machine. Table 1 shows the results of measuring tensile strength and elongation, flexural modulus, and ozone resistance using these test pieces. It has become clear that polyoctenylene rubber has poor ozone resistance, and 21-lyl butadiene rubber has poor ozone resistance and moldability.

Comparative Examples 4 to 7 Nylon 12 (Diamid L1 manufactured by Daicel-Hüls)
940) was blended with rubber in the proportions shown in Table 1, and Examples 1-
It was kneaded and molded in exactly the same manner as in No. 5, and its tensile strength and elongation, flexural modulus, and ozone resistance were measured. The results are shown in Table 1.

Claims (1)

[Claims] 1. A polyamide resin is blended with crosslinked polyoctenylene rubber and crosslinked nitrile butadiene rubber, and further α
, β-unsaturated carboxylic acid or its derivative. 2. When blending polyoctenylene rubber, nitrile butadiene rubber, and α,β-unsaturated carboxylic acid or its derivative into polyamide resin, the polyamide resin melts, the rubber melt-crosslinks, and the α,β-unsaturated 2. The method for producing a rubbery resin composition according to claim 1, which comprises a step of kneading under conditions in which a saturated carboxylic acid or a derivative thereof melts and reacts.