JPS60155247A - Flexible hose - Google Patents

Abstract

PURPOSE:To provide the titled hose having excellent resistance to heat distortion, creep and weather, by molding a compsn. consisting of a vinyl chloride resin having a high degree of polymn., a specified rubber component, a plasticizer and three stabilizers. CONSTITUTION:A high-molecular material consisting of 30-80wt% vinyl chloride resin having an average degree of polymn. of 2,000 or above (e.g., Denka Vinyl SH-250, a product of Denki Kagaku Kogyo K.K.) and 70-20wt% partially crosslinked acrylonitrile/butadiene copolymer (e.g., JSRN201, a product of Nippon Gosei Gomu K.K.). is used. 100pts.wt. said high-molecular material, 20-200pts.wt. plasticizer such as di-2-ethylhexyl phthalate, 0.05-10pts.wt. org. phosphite stabilizer, 0.05-10pts.wt. benzotriazole stabilizer and 0.05-10pts.wt. phenol stabilizer are blended together. The resulting compsn. is molded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides vinyl chloride resin, partially crosslinked acrylonide,
This invention relates to a flexible hose with excellent heat deformation resistance, creep resistance, and weather resistance formed from a composition comprising a lylubutadiene copolymer, a plasticizer, an organic phosphite compound, a benzotriazole compound, and a phenol compound.

In recent years, flexible hoses made of so-called soft vinyl chloride resin, whose main components are vinyl chloride resin and plasticizer, are lighter than im hoses, have excellent abrasion resistance and oil resistance, can be colored freely, and are weather resistant. Because it has characteristics such as good discoloration, it is used in a wide range of applications such as civil engineering, fire extinguishers, agriculture, home appliances, and gardens. These hose manufacturers and
The products of each company are introduced in detail in, for example, Rubber Industry, Vol. 19, /i63.1983JK.

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

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

On the other hand, a gasoline hose (pipe) made of a partially crosslinked acrylonitrile-citadiene copolymer blended with a vinyl chloride resin and a plasticizer system was found to be ``Basic properties of PVC formulations containing nitrile dem powder'' (3). ) J (Polymer Digest, June 1980 issue).However, although the hose with this formulation has improved phosphorus extraction resistance, it still has poor heat deformation resistance and creep resistance. However, there is also a problem with weather resistance due to the sitadiene structure in the partially crosslinked acrylonitrile-citadiene copolymer, which impairs the flexibility of coloring, which is a major feature of hoses molded from conventional soft vinyl chloride resins. There remained a drawback.

In order to solve these problems, the present inventors 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 much higher average degree of polymerization and a partially crosslinked acrylonitrile-butadiene copolymer.
A flexible hose molded from a composition containing an organic phosphite compound, benzo) IJ azole compound and a phenol compound has excellent heat deformation resistance, creep resistance,
We have discovered that the weather resistance properties are highly balanced, and have arrived at the present invention.

That is, the present invention comprises 100 parts by weight of a polymer consisting of 60-80% by weight of a vinyl chloride resin having an average degree of polymerization of 2000 or more, 70-20% by weight of a partially crosslinked acrylonitrile-citadiene copolymer, and 20-200% by weight of a plasticizer. This is a flexible hose molded from a composition consisting of parts by weight of an organic phosphite compound, a benzotriazole compound, and a phenol compound.

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. Not only is this not possible, but the mechanical strength is low, which is not preferable. Also,
The monomer composition of the vinyl chloride resin having an average degree of polymerization of 2000 or more may be composed of vinyl chloride alone or a small amount of a 1N1 or higher monomer copolymerizable with vinyl chloride.

Monomers copolymerizable with vinyl chloride include ethylene,
α-olefins such as zorozalene, vinyl esters such as vinyl acetate and vinyl stearate, vinyl ethers such as methyl-nyl ether and lauryl vinyl ether, esters of acrylic acid and methacrylic acid such as methyl acrylate and methyl methacrylate. Amides, nitriles such as methacrylamide and acrylonitrile,
It contains styrene, α-methylstyrene natonostyrenes, and polyfunctional monomers such as diallyl phthalate and ethylene glycol dimethacrylate. Also,
These vinyl chloride resins may be produced by any production method such as bulk polymerization, suspension polymerization, emulsion polymerization, and solution polymerization.

As long as the partially crosslinked acrylonitrile-citadiene copolymer used in the present invention contains a crosslinked acrylonitrile-citadiene copolymer that is insoluble in methyl ethyl ketone, there are no restrictions on the manufacturing method; or 1. copolymerization with a polyfunctional monomer such as ethylene glycol dimethacrylate. A method of increasing the reaction rate until a cross-linked acrylonitrile-citadiene compound insoluble in methyl ethyl ketone is formed, or
Any production method may be used, including a method in which unvulcanized acrylonitrile-butadiene copolymer is crosslinked using a small amount of crosslinking agent.7. (r. In general, partially crosslinked acrylonitrile-citadiene copolymers that are available include Chemi Gum N8BIA2 (manufactured by Mezdeyer Co., Ltd.), JSR
N201 (product manufactured by Nippon Gosei Gamu Co., Ltd.), ) I7Car
1422 (B, F, products manufactured by Gutdrich), etc.

The key point of the present invention lies in the ratio of the chlorinated hydrogen resin having an average degree of polymerization of 2,000 or more and the high molecular weight material consisting of the partially crosslinked acrylonitrile-butadiene copolymer. That is,
Vinyl chloride resin with an average degree of polymerization of 2000 or more 30 to 80
% by weight and a mixing ratio of 70 to 20% by weight of the partially crosslinked acrylonitrile-butadiene copolymer. If the vinyl chloride resin exceeds 80% by weight, the partially crosslinked acrylonitrile
If the butadiene copolymer is less than 20% by weight, the effect of improving the heat deformation resistance and creep resistance of the resulting flexible hose will hardly be observed; If the content of the partially crosslinked acrylonitrile-citadiene 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 range is 60 to 40% by weight of the ♂nyl chloride fruit tree B'fl and 40 to 60% by weight of the partially crosslinked acrylonitrile-citadiene copolymer.

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, 80 to 60% by weight of a vinyl chloride resin having an average degree of polymerization of 2000 or more, and 20% by weight of a partially crosslinked acrylonitrile-citadiene copolymer.
It is essential that the amount of the plasticizer be 20 to 200 parts by weight per 100 parts by weight of the polymer having a weight ratio of 70 to 70 parts by weight. If the amount of plasticizer is less than 20 parts by weight, the plasticity and creep resistance of the molded flexible hose will be poor, resulting in a rating of 2o.

If it exceeds the weight part, the mechanical strength of the flexible hose will be extremely low, which is not preferable. Note that the plasticizer here refers to those used in conventional general soft vinyl chloride resins, and specifically, phthalate esters such as di-2-ethylhexyl phthalate and dibutyl phthalate, and di-2-ethylhexyl phthalate. Azitonic acid esters such as ethylhexyl adipate, sebacic acid esters such as dibutyl sebacate, Tory 2
Examples include trimellitic acid esters such as ethylhexyl trimellitate, epoxy compounds such as epoxidized soybean oil, and polyester plasticizers. Furthermore, the present invention is characterized in that all three types of stabilizers, namely, an organic phosphite compound, a benzotriazole compound, and a phenol compound, are used in combination with the polymer and the plasticizer. A flexible hose molded from a composition lacking at least one of these three types of compounds has excellent heat deformation resistance and creep resistance, but is poor in weather resistance, particularly in weather resistance.

The organic phosphite compounds used in the present invention include:
For example, triphenyl phosphite, diphenyldecyl phosphite, tridecyl phosphite, didecyl phenyl phosphite, trioctyl phosphite, tridecyl phosphite, triotadecyl phosphite, trinonyl phosphite, trinonylphenyl phosphite, etc. Can be mentioned.

Examples of the benzotriazole compounds used in the present invention include 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-
3', 5'-tert-sotylphenyl)benzotriazole, 2-1'-hydroxy-3'-tert-butyl-5'-methyl-phenyl)-5-chloropene! /'iJ7!7'-l, 2-(2'-hydroxy-37,5/-ditertiary-butylphenyl)-5
-chlorobenzotriazole, 2-(2'-human 4'-n-octoxyphenyl)benzotriazole, and the like.

Examples of the phenolic compound used in the present invention include 2,6-diterlybutyl-4-methylphenol, 2,4-1methyl-6-tert-butylphenol, 2,2'-methylenebis(4-methyl- 6-tert-butylphenol), styrenated phenol,
2.5-1 tert-butylhide tetraquinone, n-octadecyl-3-(4'-hydroxy-3'-5'-diterlybutylphenyl)propionate, tetrakis-[methylene-3-(3', 5'- Examples include tert-butyl-4'-hydroxyphenyl) propionate comethane.

Regarding the amounts of these organic phosphite compounds, benzotriazole compounds, and phenol compounds,
For 100 parts by weight of a polymer consisting of 30 to 80% by weight of a vinyl chloride resin with an average degree of polymerization of 2000 or more and 70 to 30% by weight of a partially crosslinked acrylonitrile-citadiene copolymer, although not limited to special cases. , each 0.
05 to 10 parts by weight is preferred. If the amount is too small, the effect will be insufficient, and if it is too large, the effect will not be expressed any further and it will be economically disadvantageous. Therefore, the particularly preferable range is 1 to 8 parts by weight of the organic phosphite compound, and the benzotriazole compound. The compound skin content is 5 to 4 parts by weight, and the phenolic compound is 0.5 to 4 parts by weight.

In addition, other polymeric auxiliaries, such as ethylene-vinyl acetate copolymer, acrylic resin, chlorinated polyethylene, f
? v Urethane, chlorosulfonated polyethylene, etc. may be added. heat stabilizers, fillers, lubricants,
Foaming agents, flame retardants, pigments, etc. may also be added 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. For example, use a Henschel mixer. Also,
For flexible hoses with special shapes, injection molding, blow molding, etc. are possible.

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.

Examples 1 to 3, Comparative Examples 1 to 4 A predetermined amount of vinyl chloride resin (Denka Vinyl 5
H-250, manufactured by Denki Kagaku Kogyo Co., Ltd.) and a Ba-Zn fatty acid salt composite stabilizer (BZ-1o, r.

Hita Kako Co., Ltd.), epoxidized soybean oil (Adekasizer 0
-130p, manufactured by Adekar Gas Kagaku Co., Ltd.), calcium carbonate (Wheaton 88B, manufactured by Shiraishi Kogyo Co., Ltd.), tri(nonylphenyl) phosphite (Tsukrac TNP, manufactured by Inuyama Shinko Co., Ltd.), 2- (2'-hydroxy-5' -Methylphenyl) benzotria 1-unit (Cytbiyp, manufactured by Ciba-Ga-Year), octadecyl-3-(3,5-ditertiary-butyl-4-hydroxyphenyl) tetrabionate (Irganox 1076, Ciba-Gaia) (manufactured by Ear Inc.) was added in a predetermined amount, and the mixture was stirred and mixed at high speed until the temperature of the contents reached 60°C. Next, a predetermined amount of DOP (G2-
ethylhexyl phthalate). When the contents became smooth, cooling was started, and a predetermined amount of partially crosslinked acrylogenitrile-detadiene copolymer (Chemigam N8B-IA2, 33% acrylonitrile, manufactured by Ear Corporation) was added, and about After stirring for 5 minutes, it was taken out.

Each of the taken out compositions was kneaded with an open roll at a surface temperature of 170°C to form pellets. This beret,
90 mm φ extrusion molding machine, outer diameter 23 φ, inner diameter 1
A 911φ hose was manufactured.

The hardness, tensile strength, elongation, heat deformation resistance, and creep resistance properties of this hose were tested and evaluated and summarized in the table.

Comparative Example 5 Tests and evaluations were carried out in the same manner as in the above Examples and Comparative Examples, except that a vinyl chloride resin (Denka Vinyl S S-110-8%, Denki Kagaku Kogyosha Exhibition) with an average degree of polymerization of 1700 was used.

Record the results in the table.

Comparative Example 6 Tri(nonylphenyl)phosphite, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, and octadecyl-3-(3,5-ditertiary-dityl-4-hydroxyphenylpropionate) were added. The test and evaluation were conducted in the same manner as in Example 2, except that there was no difference.

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

(1) Hardness: Cut a square piece measuring 20mm long and 2011mm wide from the molded hose, stack two pieces, and measure using an IRHD hardness tester according to ASTM, D1415-68 (25mm hardness).
℃).

(2) Tensile strength: Measured by punching out micro-dumbbell-shaped specimens with gauge line spacing of 10 mm from stretch-formed hoses and measuring at a tensile speed of 200 mm for 1 minute (2
5℃).

(3) A sample of a heat deformation-resistant molded hose cut into a length of 20 mm was
The samples were left in a gear open state maintained at constant temperatures of 0°C, 200°C, and 220°C and 0.240°C, and the deformation state of the samples after 30 minutes was evaluated based on the following criteria.

A micro dumbbell-shaped test piece with a gauge line interval of 10 was punched out from the formed hose, a 20 g load was suspended from the lower end, and 1
Goats kept at constant temperatures of 40°C, 160°C, and 180°C - Goats that were placed in an open chamber and broke by stretching within 30 minutes〈×〉, goats that hardly deformed or broke. was marked as 〈○〉.

From the table, Comparative Example 1 has an average degree of polymerization in the polymer of 250
Since the amount of the partially crosslinked acrylonitrile-butadiene copolymer is too large relative to the vinyl chloride resin of 0.0, the tensile strength is low, and the heat deformation resistance at 240°C and the creep resistance at 180°C are poor. Comparative Example 2 is not preferable because the vinyl chloride resin is too large, so the heat deformation resistance at 200° C. or higher and the creep resistance at 160° C. or higher are poor.

Comparative Example 3 has a large hardness and lacks flexibility because the amount of DOP is too small. In Comparative Example 4, the tensile strength was extremely low due to the large amount of DOP, and the heat deformation resistance and creep resistance were extremely poor.

Comparative Example 5 is a case where a vinyl chloride resin having an average degree of polymerization of 1700 is used, and the heat deformation resistance at 220°C or higher and the creep resistance at 180°C are poor.

It can be seen that Examples 1 to 3, which are flexible hoses of the present invention, have good tensile strength and excellent heat deformation resistance and creep resistance.

Next, the hoses of Examples 1 to 6 and Comparative Example 6 were
A sample cut into 00 m5+ was aged using a sunshine weatherometer at 50° C. for 200 hours, and then the discoloration of the sample was evaluated by visual observation.

The sample of Comparative Example 6 had turned yellow, but in the samples of Examples 1 to B, which are the present invention, no discoloration was observed.
It was good.

Patent Applicant Denki Kagaku Kogyo Co., Ltd. Procedural Amendment 1, Indication of Case Patent Application No. 10776 of 1987 2, Name of Invention Flexible Hose 3, Relationship with the Amendment Person Case Patent Applicant Address Tokyo 1-4-1, Yurakucho, Chiyoda-ku, Detailed Description of the Invention, Column 5, Contents of Amendment 1) "1 tridecyl phosphite" on page 9, line 6 is corrected to "tridodecyl phosphite."

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 consisting of 70 to 20 parts by weight of a partially crosslinked acrylonitrile-butadiene copolymer, 20 to 200 parts by weight of a plasticizer, an organic phosphite compound, a benzotriazole compound, and a phenol compound. Flexible hose molded from the composition.