JPS63225645A - Rodent-repellent flame retardant organic high-molecular composition - Google Patents

Abstract

PURPOSE:To provide the title compsn. having an excellent rodent-repellent effect and suitable for use in the production of insulated wires having a sheath layer composed of the compsn. of the present invention, consisting of a non- halogenated org. high-molecular material, a halogenated org. flame retarder and a specific amount or move of a microencapsulated cycloheximide. CONSTITUTION:The title compsn. contains a non-halogenated org. high-molecular material (A) (e.g., styrene/butadiene copolymer rubber, etc.), a halogenated org. flame retarder (B) (e.g., decabromodiphenyl ether, etc.) and a microencapsulated cycloheximide (C) in such a proportion that the amount of the compd. C is at least 0.05pts.wt. in terms of cycloheximide per 100pts.wt. compd. A. Since cycloheximide is microencapsulated; it is not contacted directly with the compd. B, even though the org. high-molecular material contg. the compd. B is blended with the compd. C and heated at a high temp. Thus, it is decomposed only slightly and has an excellent rodent-repellent effect. The compsn. is suitable for use in the production of rodent-repellent, flame-retardant insulated wires having a sheath layer composed of said compsn.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a flame-retardant organic polymer composition having electrical resistance.

[Conventional technology and problems]

Cycloheximide is known as a type of antistatic agent to protect electrical wires, cables, pipes, building materials, and various equipment from heavy writing.

However, according to the experience of the present inventors, cloheximide is easily thermally decomposed and is particularly useful when added to organic polymer compositions in which halogen coexists, especially organic polymer compositions that have been made flame retardant with halogen-based flame retardants. It has the disadvantage that it is more easily thermally decomposed when it is heated to high temperatures during processing or vulcanization. Therefore, conventionally, in order to give the above-mentioned flame retardant composition the desired electrical protection performance, a large amount of cycloheximide has been added in advance in anticipation of the loss due to thermal decomposition in various steps leading up to the final molded product. Since it has been added to the formulation, it has been extremely disadvantageous in terms of cost.

[Means for solving problems]

The present inventors conducted various studies to solve the problems of the above-mentioned prior art, and as a result, they developed the present invention.

That is, the present invention comprises a non-halogenated organic polymer, a halogenated organic flame retardant, and microencapsulated cycloheximide, and the amount of microencapsulated cycloheximide is at least 0.05 cycloheximide per 100 parts by weight of the non-halogenated organic polymer. The present invention relates to a nail-proof flame-retardant organic polymer composition, characterized in that it contains parts by weight.

[Effect]

In the present invention, cycloheximide is used in a microencapsulated state. Therefore, since cycloheximide is covered by the capsule wall material and protected from the external environment, even if it is blended into an organic polymer containing a halogenated organic flame retardant and heated to a high temperature, it will not interact with the halogenated organic flame retardant. There is no direct contact (therefore, the decomposition is extremely slight, and this makes it practical to make non-halogenated organic polymers flame retardant with halogenated organic flame retardants, which have a high flame retardant effect. increases.

[Detailed description of the invention]

Examples of non-halogenated organic polymers include polyethylene, polypropylene, olefin homopolymers such as poly-4-methylpentene, ethylene-propylene copolymers, ethylene-propylene-diene ternary copolymers, and ethylene-vinyl acetate. copolymers, olefin copolymers such as ethylene-methyl acrylate copolymers, ethylene-methyl acrylate copolymers, natural rubber, butyl rubber, isoprene rubber, styrene-butadiene-copolymer rubbers, acrylonitrile-butadiene-copolymer rubbers, etc. Examples include rubber.

Examples of halogen flame retardants include decabromodiphenyl ether, decabromodiphenyl thioether, polybrominated bisphenol A, polybrominated bisphenol S1 dechlorane plus 25, chlorinated paraffin, and tetrabromodiallyl phthalate. A fuel agent is preferred.

As microencapsulated cycloheximide,
For example, cycloheximide dissolved or dispersed in a solvent is encapsulated with a microcapsule wall material made of a synthetic resin.

Particularly preferred is one produced by interfacial polymerization of a capsule wall material prepared with an oil/water emulsion.

Examples of the solvents that can be used include alcohols, ketones, ethers, aliphatic hydrocarbons, aromatic hydrocarbons, mineral oils, and acid esters.

In addition, examples of the above-mentioned capsule wall agents include urea resin,
Melamine resins, urea/melamine mixed resins, phenolic resins, polyamides, polyesters, polyurethanes, polyurethanes, etc. are preferred, and melamine resins and polyamide resins are particularly preferred.

Microencapsulated cycloheximide having an average particle size in the range of 1 to 80 μm, particularly 3 to 50 μm can be suitably used. The amount of cycloheximide itself included in the microcapsule is about 0.7 to 20% by weight, preferably 2 to 20% by weight, based on the total weight of the microcapsule.
The range is about 10% by weight. Examples of commercial products of such microencapsulated cycloheximide include, for example, Naramycin Microcapsule-D80 (manufactured by Tanabe Seiyaku Co., Ltd.).

The amount of microencapsulated cycloheximide used can be significantly reduced compared to the case of using crystalline cycloheximide for the above reasons, but it should be at least 0.05 in terms of cycloheximide per 100 parts by weight of non-halogenated organic polymer.
parts by weight, preferably 0.05 to 2.0 parts by weight, especially 0.05 to 2.0 parts by weight.
It is blended in an amount of 1 to 1.0 parts by weight.

If the amount is less than 0.05 part by weight, it will be difficult to achieve a sufficient thread-proofing effect even if microencapsulated.
．． If more than 0 parts by weight is used, a saturation phenomenon is observed in the anti-yarn effect.

The thread-proofing composition of the present invention is stabilized against heat because the thread-proofing cycloheximide is protected by a microcapsule wall material, and is therefore generally used as the base organic polymer of the composition. The composition of the present invention can be vulcanized using a crosslinking agent or a vulcanizing agent under normal temperature and time conditions, and the composition of the present invention may also contain carbon black, talc,
Clay, calcium carbonate, metal oxides, lubricants, anti-aging agents, oils, waxes, fillers, softeners, and other compounding agents commonly used for non-halogenated organic polymers may be appropriately added.

〔effect〕

The composition of the present invention includes predetermined amounts of microencapsulated cycloheximide, a halogenated flame retardant, and a non-halogenated organic polymer in a roll mill, a Henschel mixer, a Banbury mixer, a blender, a mixtruder, and a kneader.
After mixing and preparing the mixture using an extruder, it can be easily coated continuously into electric wire coatings or various other molded products.

If necessary, these molded products can be vulcanized by any suitable method such as steam crosslinking, continuous infrared crosslinking, hot air crosslinking, molten salt crosslinking, or leaded crosslinking. Since it exhibits a thread effect, it is particularly suitable for producing insulated wires having a sheath layer made of the composition of the present invention.

〔Example〕

Hereinafter, the present invention will be explained in more detail with reference to Examples and Comparative Examples.

Examples 1 to 4, Comparative Examples 1 to 2 Ethylene propylene rubber compositions shown below (basic formulation
) and a low-density polyethylene composition (basic formulation ■), and added to them ordinary, i.e., non-microencapsulated, cycloheximide (using naramycin manufactured by Tanabe Seiyaku Co., Ltd.).
abbreviated as n-CHI) or microencapsulated cycloheximide (using naramycin microcapsules-D80 manufactured by Tanabe Pharmaceutical Co., Ltd. with a cycloheximide content of 8% by weight,
? (abbreviated as IC-Cl11) was added and rolled in two rolls.
Those based on ethylene propylene rubber compositions have a temperature below 80°C, and those based on density polyethylene compositions have a temperature of 1
Each was kneaded at 30°C to obtain an anti-nail composition.

The content as cycloheximide was 0.35 parts by weight in Example 1, Example 3, Comparative Example 1 and Comparative Example 2, and 0.20 parts by weight in Example 2 and Example 4.

Ethylene propylene rubber Ethylene propylene rubber (Note 1), too much weight 11 parts Zinc oxide... 5 #Stearic acid... 1 #Talc
... 60 Antimony dioxide
... 10 Decabromodiphenyl ether... 30 Process oil... 1
0 #Dicumyl peroxide... 2.7〃Sulfur...0.32#-・Polyethylene low density polyethylene (Note 2)...1 (10 parts by weight Decabromodiphenyl ether... 15 #Chlorinated Paraffin... 15 #Antimony dioxide
... 10 Dicumyl peroxide ・
・・・ 2〃Zinc stearate ・・・
2 〃Triaryl isocyanurate... 1 #
Note 1 - JSREP21 manufactured by Japan Synthetic Rubber Co., Ltd.Note 2: Yucalon ZF-36 manufactured by Mitsubishi Yuka Co., Ltd.Among the compositions thus obtained, those based on ethylene propylene rubber compositions were pressed at 160°C for 30 minutes. - mostly those based on density polyethylene compositions at 170°C, 4
Each was vulcanized and molded under pressing conditions for 5 minutes to form a sheet with a thickness of 1 dragon.

Table 1 shows the residual rate of cycloheximide and the results of the thread-proofing test conducted on each sheet. The method for quantifying cycloheximide and the nail-proofing test are as shown below.

[Method for quantifying cycloheximide]

Precisely weigh 0.5 to 2 g of the sample, place it in a 100af volumetric flask, add 20 sJ of tetrahydrofuran, and dissolve at about 50°C while applying mechanical vibration using an ultrasonic cleaner. After cooling, add Methyl Cellsolve 20-, shake well, and then carefully heat in boiling water for 60 minutes. After cooling, accurately add the internal standard solution (ethyl roseoxybenzoate in acetonitrile?&), gradually add water to make exactly 100a7 while shaking well, filter through a membrane filter, and add the filtrate to the sample solution. shall be. Separately, a cycloheximide standard weighed accurately is made into an aqueous solution, and methyl cellosolve and an internal standard solution are added thereto to form a standard solution.

20 μl of the sample solution and standard solution are measured by liquid chromatography under the following conditions, and the amount of cycloheximide is determined from the ratio of the peak area of the sample solution to the peak area of the internal standard.

Detector: Ultraviolet absorption photometer (measurement wavelength is 210 nm) Column: Stainless steel tube with an inner diameter of about 4 fi and a length of about 15 cm filled with 5-10 μm of octadecyl silica gel Mobile phase: Water/acetonitrile mixture (3: 1) [Setting resistance test method] A sample sheet of about 75 x 150 x 1 sheet was used to wrap the trial solid feed, and the surrounding area was stapled to prepare a sample. Three Wistar rats and a sample were placed in a cage that could be constantly supplied with water for 24 hours, and left overnight to examine whether or not there was any feeding damage to the sample. If the sample sheet and the solid feed inside were eaten, it was indicated as food damage, and if the sample sheet only had tooth marks, it was indicated as no food damage.

[Margin below]

Table 1

Claims (2)

[Claims] (1) Consisting of a non-halogenated organic polymer, a halogenated organic flame retardant, and microencapsulated cycloheximide, and containing at least 0.05 parts by weight of microencapsulated cycloheximide per 100 parts by weight of the non-halogenated organic polymer. A corrosion-resistant and flame-retardant organic polymer composition characterized by comprising: (2) The corrosion-resistant, flame-retardant organic polymer composition according to claim (1), wherein the halogen-based organic flame retardant is a chlorine-based flame retardant.