JPS60195138A - Flexible hose - Google Patents

Abstract

PURPOSE:A flexible hose having improved heat distortion resistance, creep resistance, and weather resistance, obtained by molding a composition consisting of a vinyl chloride resin having high average polymerization degree, a partially crosslinked acrylonitrile-butadiene copolymer, a plasticizer and a nickel dialkyl dithiocarbamate. CONSTITUTION:(A) 100pts.wt. high polymer comprising 30-80wt%, preferably 40-60wt% vinyl chloride resin having >=2,000 average polymerization degree and 70-20wt%, preferably 60-40wt% partially crosslinked acrylonitrile-butadiene copolymer is blended with (B) 20-200pts.wt. di-2-ethylhexyl phthalate, dibutyl phthalate, etc. as a plasticizer, and (C) 0.5-10pts.wt., preferably 1-5pts.wt. nickel dialkyl dithiocarbamate as a stabilizer in a dry state, granulated, pelletized, molded by extrusion molding, etc. to produce a flexible hose.

Description

Detailed Description of the Invention [Industrial Field of Application] The present invention provides a heat-resistant product molded from a composition consisting of a vinyl chloride resin, a partially crosslinked acrylonitrile-butadiene copolymer, a plasticizer, and dialkylsothiorupamate nickel. This invention relates to a flexible hose with excellent deformability, creep resistance, and weather resistance.

[Prior art]

In recent years, flexible hoses molded from so-called soft vinyl chloride resin, whose main ingredients are vinyl chloride resin and plasticizer, have been developed. Compared to rubber hoses, flexible hoses have been developed, which have characteristics such as being lighter and having superior abrasion resistance, oil resistance, and weather resistance. It is used for a wide range of purposes, including civil engineering, fire extinguishers, agriculture, home appliances, and gardens. For information on these hose manufacturers and their products, see, for example:
“Rubber Industry, Vol. 19, N[L 3
．． It is introduced in detail in 1983 J.

However, flexible hoses made of general soft vinyl chloride resin have inferior heat deformation resistance under high-temperature conditions and rigid creep resistance compared to vulcanized rubber, so their range of use and applications are limited. was.

Therefore, Japanese Patent Publication No. 58-25347 proposes a tube molded from a partially crosslinked vinyl chloride resin composition, but compared to rubber, the heat deformation resistance and creep resistance are still unsatisfactory. Further improvements were required.

On the other hand, a gasoline hose (Noquizo) made of a partially cross-linked acrylonitrile-butatsuene copolymer blended with a vinyl chloride resin and plasticizer system was found to have the following properties: 3) J (
Polymer Digest, June 1980 issue).

However, although the hose with this formulation has improved gasoline extraction resistance, the heat deformation resistance and 111'1 creep resistance are still insufficient, and the butadiene structure in the partially crosslinked acrylonitrile-butadiene copolymer However, there remained the drawback that the weather resistance, which is a major feature of conventional hoses molded from soft vinyl chloride resins, was impaired.

[Purpose of the Invention] In order to solve these problems, the present inventors have conducted intensive studies on materials that have all the characteristics of heat deformation resistance, creep resistance, and weather resistance. As a stabilizer, it is added to a polymer consisting of a vinyl chloride resin with a specific average degree of polymerization much higher than 800 to 1300 and a partially crosslinked acrylonitrile-butatsuene copolymer.
It was discovered that a flexible hose molded from a composition containing dialkyldithiocarbamic acid has highly balanced characteristics of heat deformation resistance, severe creep resistance, and weather resistance, and the present invention was achieved.

[Structure of the invention]

That is, the present invention uses 100 parts by weight of a polymer consisting of 30 to 80% polyvinyl chloride resin having an average degree of polymerization of 2000 or more, 70 to 20% by weight of a partially crosslinked acrylonitrile-butadiene copolymer, and 20 to 200 parts by weight of a plasticizer. This is a flexible hose molded from a composition whose main components are parts by weight of nickel dialkyldithiocarbamate and 0.5 to 10 parts by weight of nickel dialkyldithiocarbamate.

The average degree of polymerization of the vinyl chloride resin used in the present invention is
Must be 2000 or more.

If the average degree of polymerization is less than 2000, a flexible hose with excellent heat deformation resistance and creep resistance, which is the objective of the present invention, will not be obtained, regardless of the combination of other partially crosslinked acrylonitrile-butadiene copolymers, plasticizers, etc. It is not desirable because it is either unobtainable or has low mechanical strength. I cut it,
The monomer composition of the vinyl chloride resin with an average degree of polymerization of 2000 or more may be composed of vinyl chloride alone or a small amount of one or more monomers copolymerizable with vinyl chloride. do not have.

Monomers copolymerizable with vinyl chloride include ethylene,
α-olefins such as propylene, vinyl ethers such as vinyl acetate, hinyl stearate (D vinyl esters, methyl vinyl ether, 5') rubinyl ether, acrylic acid and methacrylic acid such as methyl acrylate, methyl methacrylate, etc. Esters, amides such as methacrylamide and acrylonitrile, ='l
-IJ compounds, styrenes such as styrene and α-methylstyrene, and polyfunctional monomers such as soaryl phthalate and ethylene glycol dimethacrylate. In addition, the manufacturing method of these vinyl chloride resins is as follows:
Bulk polymerization, μ name, seed tongue / Tomoe Ire Nozomi, Kai, Fuku
〃υ17 it h μ (He1d h The manufacturing method described above may be adopted.

Partially crosslinked acryloni l-IJ sil- used in the present invention
The production method of the Tatsuene copolymer is not limited as long as it contains a crosslinked acrylonitrile-butanoene copolymer that is insoluble in methyl ethyl ketone. A method of copolymerizing with a monomer, a method of increasing the reaction rate by forming a crosslinked acrylonitrile-butadiene copolymer that is insoluble in methyl ethyl ketone, or a method of increasing the reaction rate by using a small amount of cross-linking agent to obtain a Any production method may be used, such as a method of crosslinking a vulcanized acrylonitrile-butadiene copolymer. In general, partially crosslinked acrylonitrile-butadiene copolymers that are available include Chemigam N8BIA2 (manufactured by Gutdeyer), JS
RN201 (product manufactured by Japan Synthetic Rubber Co., Ltd.), Hycar1
422 (B, F, parts manufactured by Gutdrich), etc.

The key point of the present invention lies in the ratio of the vinyl chloride resin having an average degree of polymerization of 2,000 or more and the polymer consisting of the partially crosslinked acrylonitrile-butatsuene copolymer. That is,
Vinyl chloride resin with an average degree of polymerization of 2000 or more 30 to 80
This is a mixing ratio of 70 to 20 double heirlooms and partially crosslinked acrylonitrile-butadiene copolymer. The vinyl chloride resin is partially cross-linked acrylonitrile which exceeds 80 weight heredity.
When the butadiene copolymer content is 20% by weight or less, almost no effect of improving the heat deformation resistance and creep resistance of the resulting flexible hose is observed; If the weight of the crosslinked acrylonitrile-butadiene copolymer exceeds 70% by weight, the mechanical strength and elongation of the hose will be low and the object of the present invention will not be achieved. Preferably, the vinyl chloride resin has 60 to 40 densities and the partially crosslinked acrylonitrile-butatsuene copolymer has 40 to 60 densities.

Next, what is important in the present invention is the above-mentioned polymer 100
It is the amount of plasticizer based on parts by weight. That is, a vinyl chloride resin with an average degree of polymerization of 2000 or more, 80 to 30 polyesters, and a partially crosslinked acrylonitrile-butadiene copolymer, 20
It is essential that the plasticizer be used in an amount of 20 to 200 parts by weight per 100 parts by weight of the polymer consisting of 70 to 70 parts by weight.

If the amount of plasticizer is less than 20 M parts, the flexibility and creep resistance of the molded flexible hose will be poor, and if it exceeds 200 parts by weight, the mechanical strength of the flexible hose will be significantly low, so it is preferable. do not have. Note that the plasticizer here refers to those used in conventional general soft vinyl chloride resins, specifically,
Phthalate esters such as di-2-ethylhexyl phthalate and dibutyl phthalate, asobine-branched esters such as di-2-ethylhexyl adishate, sebacin cough esters such as butyl sebacate, tri-2-ethylhexyl trimellitate, etc. Examples include trimellit W esters, epoxy compounds such as epoxidized soybean oil, and polyester plasticizers. Furthermore, the present invention is characterized in that nickel dialkyldithiocarbamate is blended with the above-mentioned polymer and plasticizer as a foot agent. Nickel dialkyldithiocarbamate is made of a vinyl chloride resin with an average degree of polymerization of 2000 or higher, 80 to 30 polyesters, and a partially crosslinked acrylonitrile-butanoene copolymer 2.
It is essential that the amount is 0.5 to 10 parts by weight per 100 parts by weight of the polymer consisting of 0 to 70 parts by weight. If the amount is too small, the effect will be insufficient, and if it is too large, the effect will not be achieved any further, which is economically disadvantageous.

A particularly preferred range is 1 to 5 parts by weight.

Examples of the nickel dialkyldithiocarbamate used in the present invention include nickel dimethyldithiocarbamate, nickel diethylsothiocarbamate, nickel sopropyldithiocarpate, nickel soisopropyldithiocarpamine, nickel sobutylsothiocarbamate,
Examples include nickel dicyclohexylsothiorubamate.

Further, other polymeric auxiliaries such as ethylene-vinyl acetate copolymer, acrylic resin, chlorinated polyethylene, polyurethane, chlorosulfonated polyethylene, etc. may be added. Flame retardants, pigments, etc. may be added to heat stabilizers, fillers, lubricants, and foaming agents as necessary.

The composition used for the flexible hose of the present invention can be molded in the same process as conventional soft vinyl chloride resin compositions. The tri-blend powder may be tri-blended using a Henschel mixer, a blender, etc., and the tri-blend powder may be extruded immediately or extruded after being granulated into pellets. For flexible hoses with special shapes, injection molding, blow molding, etc. can be used.

[Embodiments of the invention]

In order to further facilitate the understanding of the present invention, the present invention will be specifically explained below using Examples and Comparative Examples, but the present invention is not limited by these.

Examples 1-3. Comparative Examples 1 to 4 In a Henschel Super Mixer, a predetermined amount of vinyl chloride resin (Denka Vinyl 5H) with an average degree of polymerization of 2500 was added as shown in the table.
-250, manufactured by Denki Kagaku Kogyo Co., Ltd.) and a Ba-Zn fatty acid salt composite stabilizer (BZ-100J).

Katsuta Kako Co., Ltd.), epoxidized soybean oil (ADEKASIZER 0)
-1307 manufactured by Adeka Argus Chemical Co., Ltd.), charcoal [calcium (Whiten SSB '1 manufactured by Shiraishi Kogyo Co., Ltd.), nickel dibutyl dithiocarbamate (manufactured by Tsurank NEC, Ohmukai Shinko Co., Ltd.), and carbon black (Mitsubishi Carbon Black≠45, Mitsubishi Chemical Add a predetermined amount of Kogyo Co., Ltd. m) and continue to stir and mix until the temperature of the contents reaches 60°C.

Next, add a predetermined amount of DOP (di-2-ethylhexyl phthalate). When the contents became coarse, cooling was started, and a predetermined amount of partially crosslinked acrylonitrile-butadiene copolymer (Chemigum N8B-IA2, 33% acrylonitrile, manufactured by Gutdeyer) was added,
After stirring for about 5 minutes, it was taken out.

The respective compositions taken out were kneaded with open rolls with a surface temperature of 170°C to form pellets.

This pellet ff is supplied to a 90 mmφ extrusion molding machine,
A hose with an outer diameter of 23 mm and an inner diameter of 19 mm was manufactured.

The hardness, tensile strength, elongation, heat deformation resistance, cutting creep resistance, and weather resistance (elongation retention) of this hose were tested and evaluated, and the results are summarized in the table.

Comparative Example 5 Except for using a vinyl chloride resin (Denka Vinyl 5H-170, manufactured by Denki Kagaku Kogyo Co., Ltd.) with an average degree of polymerization of 1700,
Tests and evaluations were conducted in the same manner as in the above Examples and Comparative Examples. Record the results in the table.

Comparative Example 6 Test and evaluation were carried out in the same manner as in Example 2 except that nickel dibutyldithiocarbamate was not added.

The test methods and evaluation methods in the table were as follows.

(1) Hardness: Cut out square strips measuring 20-1 x 20 m from the molded hose, stack the two pieces together, and measure using an IRHD hardness tester in accordance with ASTM D1415-68. (25
℃).

(2) Tensile strength, measured by punching out a micro-dumbbell-shaped test piece with a stretch-molded hose frame and a gauge line interval of 10 holes, and measuring at a tensile speed of 200 ra/min (2
5℃).

(3) A sample obtained by cutting a heat-deformable molded hose into 20 pieces of length,
The sample was left in a gear oven kept at constant temperatures of 0°C, 200°C, 220°C, and 240°C, and the deformation state of the sample after 30 minutes was evaluated based on the following criteria.

A micro-dumbbell-shaped test piece with a gauge line interval of 10 m was punched out from the molded hose, and a load of 202 was suspended from the lower end.
Placed in a gear oven kept at a constant temperature of 40℃, 160℃, and 180℃, those that broke due to stretching within 30 minutes are marked <x>, and those that hardly deform or break are It was ku○〉.

(5) Weather resistance (elongation retention, %) The same micro dumbbell test piece as in (2) was aged at 50°C for 200 hours using a Sunshine Weather-Ometer.
A tensile test was conducted at a tensile speed of 200 mm/min, and the residual ratio (%) relative to the elongation in (2) was determined.

〔Effect of the invention〕

It can be seen that the flexible hose of the present invention has significantly superior heat deformation resistance at high temperatures, creep resistance, and weather resistance that were not obtained with conventional flexible hoses made of thermoplastic materials. Therefore, it is suitable for civil engineering, commercial, garden, and other industrial flexible hoses.

Patent applicant Denki Kagaku Kogyo Co., Ltd.

Claims (1)

[Claims] Vinyl chloride resin with an average degree of polymerization of 2000 or more 30 to 80
100 parts by weight of a polymer B1 consisting of 70 to 20 parts by weight of a partially crosslinked acrylonitrile-butatsuene copolymer, 20 to 200 parts by weight of a plasticizer, and 0.5 to 10 parts by weight of nickel soalkyldithiolupamate. A flexible hose molded from a composition containing the main ingredients.