JPS6017414B2 - Flame-retardant polyurethane composition for filling penetrations of electric wire cables - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a flame-retardant polyurethane composition for filling penetrations of electric wires and cables, which has excellent flame retardancy, watertight sealing properties, and disassembly properties.

When sealing the wall or floor penetrations of electric wire cables to prevent the spread of fire or the flow of water, there is a method of filling the gaps with a putty-like sealant. Packing putty can be difficult. In such cases, a method of injecting a fluid compound that hardens at room temperature is used.

Conventionally, compounds based on eboxy resin or polyurethane resin have been used as this type of compound, but there are few compounds with sufficient performance. In other words, when relocating or adding to an existing electric wire cable, it is necessary to dismantle the penetrating seal, but epoxy resin-based compounds cure economically and do not damage the electric wire cable. Difficult to disassemble. Conventional polyurethane-based compounds that have been used for this type of application are urethane-based compounds consisting of a TD1 (tolylene diisocyanate) prepolymer, a polyether polyol, and a curing catalyst, in which a flame retardant is blended. When using a TDI prepolymer as an isocyanate component, the mixing ratio of the prepolymer and polyol is determined based on the equivalent weight of isocyanate groups and hydroxyl groups contained in each, and the isocyanate content in the prepolymer (usually 2 to 7%) is relatively small,
The proportion of polyol used is reduced.

For this reason, the amount of powdered flame retardant that can be blended while maintaining fluidity into a urethane system that uses a small proportion of low-viscosity polyol to high-viscosity polymer is limited to a small range, resulting in excellent flame retardancy. cannot be granted.

In order to cause the TDI prepolymer and polyol to react at room temperature, it is necessary to add a catalyst, and although the curing speed can be adjusted to some extent by changing the amount of catalyst, the amount of catalyst must be adjusted so that the curing occurs within a practical time (about 2 hours). However, the disadvantage is that the initial viscosity increases significantly and the potency time is short.

The present invention improves the above-mentioned drawbacks of the prior art and provides a polyurethane composition with good pouring workability, curing properties, high flame retardancy, sealing properties, and resistance to disassembly.

The present invention (1) has a molecular weight of 200 as the isocyanate component.
-1000, using a liquid polyisocyanate at 25°C.

These polyisocyanates are of high isocyanate content, on the order of 10-35%, allowing the use of significantly higher amounts of polyol than TDI prepolymers, and are themselves generally of low viscosity. The reason for setting the molecular weight to 200 or more is that isocyanate compounds with small molecular weights, such as TD1 (molecular weight 174), have a high vapor pressure at the handling temperature, and there is a high risk of health problems due to inhalation of the vapor, and they may be poisonous or poisonous. Special consideration is required for this,
This is because the handleability is inferior.

The reason for limiting the molecular weight to 1000 or less is that as the molecular weight increases, the viscosity also increases, the isocyanate content decreases, and the proportion of low-viscosity polyol to be combined decreases, making it impossible to achieve the intended purpose of the present invention. It is from.

The polyisocyanate that can be used in the present invention is a liquefaction isomer of diphenylmethane diisocyanate (MDI) (molecular weight approximately 250, trade name Millionate MTL, ISONA
Polymethylene polyphenylysocyanate (molecular weight 360 to 400, trade name: Millionate M, PAPI, etc.) is a condensate that has been purified and pretreated with MDI (TE14, MDI-LD, etc.). Polyisocyanates obtained by addition-reacting these isocyanates with divalent polyols in a proportion whose average molecular weight does not exceed 1,000 can also be used. Further, a prepolymer having a large molecular weight such as a TDI prepolymer may be used in combination as long as the purpose of the present invention is not impaired. The present invention '2) uses castor oil as a polyol component.

Since castor pond contains triglyceride of ricinoleic acid as its main component, it can be considered a trivalent polyol. The polyisocyanate and castor oil specified in the present invention react at room temperature without a catalyst to form a cured product with high electrical insulation.
Adheres well to metal and plastic.

Since castor oil has a smaller amount of oxygen in its molecules than polyether polyols, it tends to be easier to make flame retardant, but the present invention does not at all deny the use of polyols other than castor oil.

The present invention is based on the above-mentioned [11 polyisocyanate and {2' castor oil watan component [1] 10 parts by weight,
2500, and 50 to 30 parts by weight of a halogenated flame retardant [B] containing liquid chlorinated paraffin is combined. As the halogen-based elutriation agent, liquid chlorinated paraffin is used as an essential ingredient, but powdered salt puff, hexabromobenzene,
Hexabrom diphenyl ether, decabrom diphenyl ether, dechlorane (a chlorinated flame retardant manufactured by Hooker Chemical Company), etc. may be used in combination with the liquid salt para. The reason why liquid chlorinated paraffin is used as an essential component is that it can increase the amount of powdered retardant that can be added to the compound, and that it has the effect of imparting plasticity to the cured product and improving disassembly. In the present invention, 50 to 30 parts by weight of the inorganic retardant component [m] are blended with 100 parts by weight of the urethane component [1].

Inorganic retardant components include hydrated alumina, hydroxides such as magnesium hydroxide and calcium hydroxide, borates such as magnesium borate and zinc borate, phosphorus compounds such as ammonium polyphosphate and phosphate frit, Examples include antimony trioxide, and general inorganic powders such as calcium carbonate, talc, clay, quartz powder, mica powder, and titanium white may also be used. Furthermore, the present invention provides a urethane component [1
] 0.2 to 10 parts by weight of fibrous filler [N]
2 parts by weight is used as an essential ingredient.

Fibrous fillers are effective in preventing dripping of cured polyurethane products when exposed to flame.
If it is less than 0.2 parts by weight, a sufficient effect cannot be obtained, and if it is more than 2 parts by weight, the fluidity of the compound will be reduced, so the range is from 0.2 to 2 parts by weight.

As the fibrous filler, in addition to inorganic fibers such as glass fibers, rock wool, and carbon fibers, organic fibers that are carbonized and retain their fibrous shape even after combustion (for example, phenolic resin fibers such as Kynol (trade name)) can be used.

In addition, the composition of the present invention may contain a stabilizer for a halogen compound, a liquid filler having good compatibility with urethane, a coloring agent, and other additives, if necessary.

Next, the present invention will be specifically explained with reference to Examples.

Example 1 A urethane component consisting of 30 parts by weight of MDI pre-purified condensate polyisocyanate (trade name Millionate MR-200) and 7 parts by weight of castor oil was added with 11 parts of liquid chlorinated paraffin (50% chlorine content). parts by weight, 4 parts by weight of decabromodiphenyl ether, 8 parts by weight of hydrated alumina, 5 parts by weight of phosphate frit, 1 part by weight of zinc borate, 1 part by weight of antimony trioxide, 5 parts by weight of glass fiber, A flame-retardant polyurethane composition was prepared by mixing 5 parts by weight of liquid epoxy resin Epiquat 828 as a stabilizer for halogen compounds.

This composition had an initial viscosity of 1500 p, good fluidity, and was cured to the touch at room temperature for about 8 hours. After curing for one day at room temperature, the oxygen index was measured and found to be 35. As a result of testing the combustibility of a hardened sheet with a width of 1 x 5 x 5 x 12 x 12 x 12 x 12 x 12 x 12 x 100 x 120 x 120 x 120 x 120 x 120 x 120 x 120 x 500 x 120 x 120 x 120 x 120 x 120 x 500 x 500 x 500 x 12 may. The fire self-extinguished as soon as the flame was removed. In addition, to simulate the floor penetration part of the cable, as shown in the attached drawing, the east of the vinyl sheath cable 2 (outer diameter 1 length x 20 pieces) was passed through the conduit pipe 1 with an inner diameter of 120 legs, and the lower end was covered with putty. 3, and polyurethane 4 having the above composition was injected and cured at room temperature for one day.

Next, a heat cycle of 4 hours at 80 qo and 4 hours at 20 pm was repeated 1M times.

After removing the putty material 3 at the lower end, the upper part was filled with water 5 to check for leakage, and it was found that there was no leakage from the interface between the pipe and the cable, and watertightness was maintained. This cured flame-retardant urethane material could be dismantled relatively easily by poking it with the tip of a screwdriver.

[Brief explanation of drawings]

The figure is an explanatory diagram of the case where the composition of the present invention is applied to a model of a floor penetration part of a cable. 1... Conduit pipe, 2... Cable, 3...
putty material, 4... polyurethane composition, 5...
···water.

Claims (1)

[Claims] 1 (1) The isocyanate component has a molecular weight of 200 to 100.
It is a polyisocyanate that is liquid at 0.25°C, (2)
For 100 parts by weight of the room temperature curable urethane component [I] whose polyol component is castor oil, (3) 50 parts by weight of the halogenated flame retardant component [II] containing chlorinated paraffin which is liquid at 25°C.
~300 parts by weight, (4) Inorganic flame retardant component [III] 5
0 to 300 parts by weight, (5) fibrous filler [IV] 0.2 to
A flame-retardant polyurethane composition for filling penetrations of electric wires and cables, characterized in that it contains 20 parts by weight as an essential component.