JPS61271710A - Fireproof polyurethane wire sheath - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a wire sheath, and more particularly to a flame-retardant polyurethane wire sheath with excellent heat resistance and hydrolysis resistance.

(Prior art and problems to be solved by the invention) Conventionally, in the field of flame-retardant wire sheaths, wire sheaths made of compositions containing flame retardants such as polyethylene, EVA, PVCl, or chloroprene have been used. However, the mold strength, elongation, and tear strength were low, and the abrasion resistance was also low, making the durability unsatisfactory.

In terms of durability, chloroprene is relatively good, but it is because it is a so-called vulcanized rubber.

It has drawbacks in terms of processability and also has low wear resistance.

PvC resin is mainly used for curl cords, etc., but it has low abrasion resistance and if the shield layer inside the sheath is thick or there are several wires, the entire body becomes hard and the curl characteristics deteriorate. It was difficult to get the curls out, and the curls tended to come off with long-term use.

In order to solve these drawbacks, it has been proposed to use polyurethane resin as the base synthetic resin, but if a polyester-type polyurethane resin is used as the polyurethane resin, the polyurethane The hydrolyzability of the resin increases, and in applications where the resin is in contact with moisture for a long period of time, it deteriorates severely and cannot be used.

Furthermore, when a polyether type polyurethane resin is used as a polyurethane resin, the heat resistance of the polyurethane resin used decreases due to the addition of a flame retardant, and the polyurethane resin also decomposes during the heat treatment when the flame retardant is mixed and added. However, there is a problem in that various physical properties deteriorate.

In order to solve the drawbacks of the prior art as described above, the present inventors
As a result of intensive research, the present invention was completed after discovering that the above-mentioned drawbacks of the prior art can be solved by using a specific polyurethane resin as the synthetic resin that is the base material for the flame-retardant wire sheath. .

(Means for Solving the Problems) That is, 1 the present invention consists of a polyurethane resin and a flame retardant, 50% by weight or more of the polyurethane resin consists of a polycarbonate polyurethane resin, and the flame retardant is approximately This is a flame-retardant polyurethane wire sheath with excellent heat resistance and hydrolysis resistance, which is blended in a proportion of 5 to 200 parts by weight.

Next, to explain the present invention in more detail, 1. The present inventor adopted a specific polyurethane resin, that is, a polycarbonate polyurethane resin, as a synthetic resin in a conventionally known flame-retardant wire sheath, and also added a flame retardant to be used in a specific proportion. By doing so.

It has excellent durability without the disadvantages of conventionally known flame-retardant wire sheaths, such as decreases in tensile strength, elongation, tear strength, abrasion resistance, and elastic modulus due to the addition of flame retardants, and is superior to conventional polyester type wire sheaths. The present inventors have discovered that a new flame-retardant polyurethane wire sheath can be obtained without deterioration in hydrolyzability like polyurethane resins and heat resistance like conventional polyether-type polyurethane resins.

In the present invention, the polycarbonate polyurethane resin used and which mainly characterizes the present invention is polyol,
Among polyurethane resins that are generally synthesized from polyisocyanate and optionally a chain extender, this is a polyurethane resin obtained by using a polycarbonate polyol as a polyol component.

The polycarbonate polyol that characterizes the above polyurethane resin is obtained by condensing a conventionally known polyhydric alcohol with phosgene, chloroacetate, dialkyl carbonate or diallyl carbonate, and can be obtained in various molecular weights.

Preferred polycarbonate polyols for obtaining the polycarbonate polyurethane resin of the present invention include 1,6-hexanediol, 1,4
-butanediol, 1.3-butanediol, neopentyl glycol, 1.5-bentanediol, or a mixture thereof, with a molecular weight of about 300-15,000 and a hydroxyl value of about 7. 5～
374 range.

Such polycarbonate polyols are preferably used alone in the production of polyurethane resins, but
It can also be used in combination with polyester polyols, polyether polyols, or polyester-bolyether polyols that are known for producing polyurethane resins.

When used in combination, the amount of other polyols as described above is preferably about 100 parts by weight or less per 100 parts of the polycarbonate polyol, and if it exceeds this range, it is difficult to obtain the desired effects of the present invention.

The polycarbonate polyurethane resin used in the present invention and which mainly characterizes the present invention is manufactured using the polyisocyanate, chain extender, catalyst, and manufacturing method itself, except for the use of the polycarbonate polyol as described above. Any known one may be used.

Any of these known organic polyisocyanates are useful in the present invention. Particularly preferred organic polyisocyanates are as follows.

Toluene-2,4-diisocyanate, 4-methoxy-
1,3-phenylene diisocyanate, 4-isopropyl-1,3-phenylene diisocyanate, 4-chloro-1,3-phenylene diisocyanate.

4-butoxy-1,3-phenylene diisocyanate, 2.4-diisocyanate-diphenyl ether, mesitylene diisocyanate, 4.4-Methylenebis(phenylisocyanate).

Shuryen diisocyanate.

1.5-naphthalene diisocyanate, benzidine diisocyanate, 0-nitrobenzidine diisocyanate, 4.4-dibenzyl diisocyanate, 1.4-tetramethylene diisocyanate, 1.6-tetramethylene diisocyanate, 1.10-decamethylene diisocyanate, 1 .4
-Cyclohexylene diisocyanate, xylylene diisocyanate, 4.4-methylenebis(cyclohexylisocyanate) -
g), 1,5-tetrahydronaphthalene diisocyanate, and the like.

Preferred chain extenders include 1, for example, 1,6-hexane glycol, 1,4-butanediol, 1,3-butanediol, 1,2-propylene glycol, ethylene glycol, diethylene glycol, neopentyl glycol, 1. Examples include 4-cyclohexylene glycol and 1,4-xylylene glycol.

Suitable catalysts also include, for example, tertiary amines such as N-methylmorpholine, N,N'-dimethylaniline, triethanolamine and the like, metals such as stannous chloride, ferric chloride, etc. Chloride or organometallic compounds such as dibutyltin di-2-ethylhexoate, butyltin dilaurate, iron acetylacetonate and the like. These catalysts are used by being dissolved or uniformly dispersed in the raw materials.

The production of the polycarbonate polyurethane resin using the above-mentioned raw materials may be carried out by conventionally known methods.

The flame retardant used in the present invention is a conventionally known material, and any conventionally known materials can be used. For example, as a metal compound, zinc borate, barium metaborate, zirconium hydroxide, water Examples include magnesium oxide, antimony trioxide, calcium sulfate, calcium hydroxide, calcium carbonate, magnesium carbonate, molybdenum trioxide, ferrocene, and sodium antimonate.

In addition, as a halogen-containing compound, Tetrabromoethane.

Tetrabromobutane, 1.2-dibromo-3-chloropropane, 1.2.3-
Bromine-containing compounds such as tribromopropane, hexabwamocyclododecane, tetrabromobenzene, decabromodiphenyl ether, bis(bromoethyl ether)tetrabromobisphenol-A, ammonium bromide; chlorinated paraffin, chlorinated polyethylene, chlorinated diphenyl Examples include chlorine-containing compounds such as.

In addition, phosphorus compounds include ammonium polyphosphate, trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, octyldiphenyl phosphate, tris(chloroethyl ) phosphate, tris(dichloropropyl) phosphate, tris(chloropropyl)
Examples include phosphorus-containing compounds such as phosphate and tris(2,3-dibromopropyl) phosphate.

In the present invention, the flame retardant as described above is used in an amount of 5 to 20 parts by weight per 100 parts by weight of the polycarbonate polyurethane resin.
It is preferable to use it in a proportion of 0 parts by weight; if it is used in an amount of 5 parts by weight, sufficient flame retardancy cannot be imparted to the resulting electric wire sheath, and if it is used in an amount exceeding 200 parts by weight, This is not preferable because various physical properties such as workability of the resulting electric wire sheath become insufficient.

The essential components of the polyurethane wire sheath of the present invention are as described above, and in addition to the polycarbonate polyurethane resin, 100 parts by weight of other polyurethane resins other than the polycarbonate polyurethane resin are added per 100 parts by weight of the polycarbonate polyurethane resin. Further, such a polyurethane resin may be a polyester type polyurethane resin or a polyether type polyurethane resin.

Furthermore, the flame-retardant polyurethane wire sheath of the present invention contains various additives used in other conventionally known flame-retardant wire sheaths, such as colorants, fillers, plasticizers, antioxidants, foaming agents, A lubricant and other substances may be added within a range that does not impair the purpose of the present invention.

(Effect) The flame-retardant wire sheath of the present invention as described above has higher tensile strength and tear strength than the resin base material used, like conventional flame-retardant resin compositions for wire sheaths. It is not inferior in wear resistance, elasticity, etc., and has various excellent physical properties similar to those of the polycarbonate polyurethane resin used, and also has good curling characteristics and processability.

In addition, while conventional flame-retardant wire sheaths using polyester-type polyurethane resin show significant deterioration due to hydrolysis when used in contact with water, the flame-retardant polyurethane wire sheath of the present invention exhibits such deterioration when used in contact with water. It has extremely excellent hydrolyzability, and unlike conventional flame-retardant wire sheaths using polyether type polyurethane resin, it has excellent heat resistance even during heat molding, and It possesses various excellent physical properties even when heated.

Therefore, the flame-retardant polyurethane wire sheath of the present invention is useful in the field of wire sheaths in all fields where flame retardancy is required, and is particularly useful in flame-retardant curl cord sheaths.

Next, the present invention will be explained in more detail with reference to Examples. Note that parts and percentages in the text are based on weight.

Example 1 Production of polycarbonate polyurethane resin (A) 359 parts of diethyl carbonate and 718 parts of 1,6-hexanediol were reacted at 120°C to 200°C for 15 hours, then cooled to 150°C and reduced pressure to 30 to 50%
Sufficiently distill off the ethanol remaining as 0-layer Hg,
797 parts of polycarbonate polyol were obtained. This polyol had a hydroxyl value of about 52.5 and a molecular weight of about 2,139.

121 parts of this polyol, 18 parts of ethylene glycol and 94 parts of MDI were added to about 80 to 1
A polycarbonate polyurethane resin (A) was obtained by reacting at 20° C. for 3 hours.

Example 2 Polycarbonate polyurethane resin obtained in Example 1 (A
) l 0 parts antimony trioxide 45 parts hexabromobenzene
45 parts lubricant (stearin ugly)
0.4 parts of the above ingredients are kneaded in a Banbury mixer,
A resin composition for a flame-retardant polyurethane electric wire sheath was obtained.

The physical properties of the obtained composition were as shown in Tables 1, 2, 3 and 84.

Furthermore, this polyurethane resin composition was made into pellets, and the core wire cross-sectional area was 6 mm'' using an extruder with a diameter of 115 and a single layer of φ.
A polyethylene insulator was coated as a sheath material to a thickness of 2.0 mm on an insulated core electric wire having a thickness of 1.5 mm. Table 5 shows the sheath appearance of the obtained polyethylene insulated flame retardant polyurethane sheathed cable.

Example 3 Polycarbonate polyurethane resin obtained in Example 1 (A
) 55 parts Polyester polyurethane resin 45 parts (Product name: Rezamin P -
7040 Dainichiseika Chemical Industry Co., Ltd. product) Antimony trioxide 45 parts Hexabromobenzene 45 parts Stearic acid
0.4 part The above components were treated in the same manner as in Example 2 to obtain a flame-retardant polyurethane resin composition for electric wire sheath.

The physical properties of the obtained composition were as shown in Tables 1, 2, 3 and 4.

Furthermore, Table 5 shows the appearance when made into a sheath in the same manner as in Example 2.

Comparative Example 1 Polyester polyurethane resin 100 parts (product name: Rezamin P-7040, product of Dainichiseika Industries Co., Ltd.) Antimony trioxide 45 parts Hexabromobenzene 45 parts Stearic acid
0.4 parts The above components were treated in the same manner as in Example 1 to obtain a comparative flame-retardant polyurethane wire sheath resin composition. The physical properties of the obtained composition were as shown in Tables 1, 2, 3 and 4.

Furthermore, Table 5 shows the appearance when made into a sheath in the same manner as in Example 2.

Comparative Example 2 Polyether polyurethane resin 100 parts (product name: Rezamin P-2040, Dainichiseika Chemical Industry Co., Ltd. product) Antimony trioxide 45 parts Hexabromobenzene 45 parts Stearic acid
0.4 parts The above components were treated in the same manner as in Example 1 to obtain a comparative flame-retardant polyurethane wire sheath resin composition. The physical properties of the obtained composition were as shown in Tables 1, 2, 3 and 4.

Furthermore, Table 5 shows the appearance when made into a sheath in the same manner as in Example 2.

Support [310415295435 Support 3 29B 422 293 4
24 Supervision 1 302 404 289
427 Rebellion 1'' 125 412 H21 copy The heat resistance was measured using a test piece (thickness o, 04~0.
05 mm, length 60++n), and was left in a gear oven at 120° C. for 400 hours.

L-Emperor-119 ni Kami-ku Kamikenjo” 11ヱ 310 4+5 302
428LLfL! 29B 422
275 43 + Le J Lo LL 304
404 187 45B stop 1u1 work 125
412 111 423 The hot water resistance was measured after being left in an atmosphere at a temperature of 70° C. and a humidity of 95% for two weeks.

Fruit' Meal 1ヱ Suitable Fruit'1 MaroL
] Compatibility ratio "Doctor L" 2
Suitable for J-J 1ヱ
Applicable book 1ヱThe above measurement is thickness 3.18■
The test was conducted according to UL94 using Maro's test piece.

Self-weight - 4 years of decay length" 11ヱ 32 Dog JLI 33 Stop 1 11 35 Stop Jmu 1ヱ 47 Wood Wear resistance measurement is based on JISK7204, taper set, wear wheel H-22, load IKg, rotation number 1.00
Measured 0 times.

Polyurethane sheath "Crush" - two-dimensional appearance

Claims (3)

[Claims] (1) Consisting of a polyurethane resin and a flame retardant, 50% by weight or more of the polyurethane resin consists of a polycarbonate polyurethane resin, and the flame retardant consists of the polyurethane resin 1
A flame-retardant polyurethane wire sheath with excellent heat resistance and hydrolysis resistance, which is blended at a ratio of about 5 to 200 parts by weight per 00 parts by weight. (2) The flame-retardant polyurethane wire sheath according to claim (1), wherein 50% by weight of the polyurethane resin ends in a polyester-type polyurethane resin and/or a polyether-type polyurethane resin. (3) The flame-retardant polyurethane wire sheath according to claim (1), wherein 50% by weight or more of the polyol component of the polycarbonate polyurethane resin is polycarbonate polyol.