JPH03281568A - Flame-retardant polyurethane resin composition - Google Patents

Abstract

PURPOSE:To provide a flame-retardant polyurethane resin composition having excellent water resistance, flame resistance, mechanical strength, flexibility, etc., by compounding a halogeno flame-retardant, antimony trioxide, etc., with a polyurethane resin. CONSTITUTION:The composition comprises (A) 100 pts.wt. of a polyurethane, (B) 1-35 pts.wt. of a halogeno flame-retardant, (C) 3-16 pts.wt. of antimony trioxide, (D) 0.1-15 pts.wt. of a compound (e.g. epoxy oleic acid) having an epoxy group in the molecule excluding the end portions thereof, and (E) 0.1-6 pts.wt. of a montan wax.

Description

[Detailed description of the invention] [Industrial application field] The present invention relates to flame-retardant polyurethane resin compositions.

[Prior Art] Polyurethane resin compositions have excellent mechanical strength, abrasion resistance, rebound resilience, flexibility, etc., and are therefore widely used as component materials for various products including wire sheathing materials. . In particular, electric wire sheath materials are used in high temperature atmospheres, humid atmospheres, and other various environments. Therefore, when a polyurethane resin composition is used for a wire sheath material, the polyurethane resin composition must have properties such as heat resistance, flame retardance, and water resistance in addition to mechanical strength and flexibility. .

Conventionally, in order to improve flame retardancy and heat resistance, polyurethane resin compositions have contained heat stabilizers such as halogen flame retardants and epoxy compounds.

[Problems to be solved by the invention] However, such polyurethane resin compositions
Poor water resistance. For this reason, electric wire sheaths using polyurethane resin compositions deteriorate after long-term use. This is because the polyurethane resin composition reacts with moisture in the air and undergoes hydrolysis. Furthermore, the epoxy compound contained in the polyurethane resin composition reacts with moisture in the air to become a sticky substance, which appears on the surface of the wire sheath.

This adhesive substance inhibits the appearance of the wire.

The present invention has been made in view of the above, and provides a flame-retardant polyurethane resin composition that has excellent water resistance, and also has excellent properties such as flame retardancy, mechanical strength, and flexibility. be.

[Means for Solving the Problem] The present invention provides 1 to 35 parts by weight of a halogen flame retardant and 3 to 3 parts by weight of antimony trioxide to 100 parts by weight of a polyurethane resin.
16 parts by weight, 0.1 to 15 parts by weight of a compound having one epoxy group in one molecule at a position other than the end of the molecule, and 0.1 to 6 parts by weight of montan wax. It is a flame-retardant polyurethane resin composition.

Here, the polyurethane resin is obtained by reacting a bifunctional polyol, a glycol, and a diisocyanate compound.

A polyurethane resin is composed of a soft block obtained by a reaction between a polyol and a diisocyanate compound, and a hard block obtained by a reaction between a glycol and a diisocyanate compound.

Bifunctional polyols include poly(ethylene adipate),
Polyester diols such as poly(1,4-butyl adipate), poly(1,6-hexane adipate), poly-ε-caprolactam, poly(hexamethylene carbonate), or polyether diols such as polyoxytetramethylene glycol, etc. used.

Glycol acts as a chain extender when synthesizing polyurethane resins. As such glycol, 1,4-butylene glycol, 1,6-hexanediol, ethylene glycol, etc. are used.

As the diisocyanate compound, 4.4'-diphenylmethane diisocyanate, 4.4=-dicyclohexylmethane diisocyanate, isophorone diisocyanate, etc. are used.

Examples of halogen flame retardants include trischloroethyl phosphate, tris(2,3-dibromopropyl) phosphate, bis(23-dibromopropyl)-dichloropropyl phosphate, triallylisocyanurate bromine compound, decabromodiphenyl ether, and tetradecabromodiphenyl phosphate. Examples include phenoxybenzene and tetrabromophthalimide. The flame retardant may be used alone or in an appropriate combination of two or more thereof. In addition, these compounding amounts are 1 to 100 parts by weight of polyurethane resin.
~35 parts by weight. This is because if the amount of flame retardant is less than 1 part by weight per 100 parts by weight of the polyurethane resin, the resulting composition will not exhibit sufficient flame retardancy, and if it exceeds 35 parts by weight, the resulting composition will Poor flexibility at low temperatures (,
This is because extrusion processability deteriorates. The amount of flame retardant is
It is particularly preferable that the amount is 8 to 23 parts by weight based on 100 parts by weight of the polyurethane resin.

Antimony trioxide, together with a flame retardant, improves the flame retardancy of the polyurethane resin composition. In addition, the blending amount of antimony trioxide is 3 to 3 to 100 parts by weight of polyurethane resin.
Set to 16 parts by weight.

This is because when the amount of antimony trioxide blended was less than 3 parts by weight per 100 parts by weight of the polyurethane resin, the resulting composition did not exhibit sufficient flame retardancy, and even when the amount exceeded 16 parts by weight, it was noticeable. This is because the flame retardant effect cannot be obtained. It is particularly preferable that the amount of antimony trioxide is 5 to 15 parts by weight based on 100 parts by weight of the polyurethane resin.

A compound having one epoxy group in one molecule at a position other than the molecular terminal contributes to the thermal stability of the polyurethane resin composition and does not react with moisture. such as epoxidized oleic acid, epoxidized linoleic acid, epoxidized luic acid, or mixtures thereof;
Epoxidized soybean oil, epoxidized linseed oil; oleic acid,
Examples include epoxidized derivatives such as esters of linoleic acid and lyluic acid; reactive diluents for epoxy resins such as alkyl glycidyl ether; and cycloaliphatic epoxy resins. These compounds may be used alone or in an appropriate combination of two or more. The compounding amount of this compound is 10% of the polyurethane resin.
It is set at 0.1 to ]85 parts by weight relative to 0 parts by weight. This is because when the compound amount was less than 0.1 part by weight per 100 parts by weight of the polyurethane resin, the resulting composition did not exhibit sufficient thermal stability, and even when the amount exceeded 15 parts by weight, it was noticeable. This is because a thermal stabilizing effect cannot be obtained.

The compounding amount of the compound is particularly preferably 3 to 12 parts by weight per 100 parts by weight of the polyurethane resin.

Montan wax is a mixture of montanic acid, mainly composed of a linear saturated carboxylic acid with a chain length of C28 to C32 and a soap ester, and has the simplified structural formula (I) shown below. . Moreover, montan wax is a component that improves the water resistance of the polyurethane resin composition.

C2a-32 C28-32 The C28-2 portion in structural formula (I) is a linear saturated carboxylic acid and is a hydrophobic group. Therefore, this portion contributes to the water resistance of the polyurethane resin composition.

Furthermore, since montan wax has external lubricity, it is also effective as a mold release agent during molding. The compounding amount of the montan wax compound is set to 0.1 to 6 parts by weight based on 100 parts by weight of the polyurethane resin. This means that the compound amount is 0 per 100 parts by weight of the polyurethane resin.
．． If the amount is less than 1 part by weight, the resulting composition will not exhibit sufficient water resistance, and if it exceeds 6 parts by weight, no outstanding water resistance effect will be obtained. The amount of montan wax blended is particularly preferably 0.4 to 4 parts by weight per 100 parts by weight of the polyurethane resin.

Further, a polyfunctional monomer can be suitably added to the composition of the present invention, and the composition can be crosslinked by ionizing radiation.

[Function] The flame-retardant polyurethane resin composition of the present invention contains 1 to 3 parts of a halogen flame retardant per 100 parts by weight of the polyurethane resin.
5 parts by weight, 3 to 16 parts by weight of antimony dioxide, 0.1 to 15 parts by weight of a compound having one epoxy group in one molecule at a position other than the end of the molecule, 0.1 part by weight of montan wax
~6 parts by weight.

The polyurethane resin portion exhibits properties such as mechanical strength, abrasion resistance, rebound resilience, and flexibility, while the halogen flame retardant and antimony trioxide exhibit flame retardancy. 1 epoxy group
A compound having one in the molecule exhibits heat resistance. Furthermore, since the epoxy group of this compound is present at a position other than the terminal end of the molecule, it is prevented from reacting with moisture and producing a sticky substance. Montan wax exhibits high water resistance when blended in a predetermined amount.

Therefore, the flame-retardant polyurethane resin composition according to the present invention exhibits heat resistance, flame retardancy, and water resistance while fully exhibiting properties such as mechanical strength, abrasion resistance, rebound resilience, and flexibility. Demonstrate your sexuality.

[Example] Examples of the present invention will be specifically described below.

Example 1 First, 100 parts by weight of ether polyurethane was used as a polyurethane resin, 10 parts by weight of trichloroethyl phosphate was used as a halogen flame retardant, 5 parts by weight of antimony trioxide, 6 parts by weight of epoxidized oleic acid, and Hoechst wax OP (Hoechst wax) was used as a montan wax. Company-made, product name) 2
Parts by weight were mixed. The resulting mixture was kneaded with a roll. Next, this mixed wire material was press-molded to obtain a sheet-like material with a thickness of 1 mm. Thereafter, the obtained sheet-like body was punched out to produce a dumbbell-shaped sample.

The obtained sample was left in a constant temperature and humidity chamber at a temperature of 80° C. and a humidity of 95% RH for 240 hours. This sample was subjected to a tensile tester to examine tensile elongation and tensile strength.

Using the test results thus obtained and the test results of the tensile elongation and tensile strength of the sample before being left for 240 hours, the moisture and heat deterioration resistance (property retention) was calculated. These results are shown in Table 1 below along with the blending amounts of each component.

Note that the moisture and heat deterioration resistance was calculated based on the following formula (II). The results are shown in Table 1 below along with the blending amounts of each component.

Moisture and heat deterioration resistance - (Test results of sample after being left/Test results of sample before being left) The results are also listed in Table 1 below.

Examples 2-7 The components shown in Table 1 below were mixed in the amounts shown in the same table.

Example 2 was carried out in the same manner as in Example 1 using the obtained mixture.
~7 samples were prepared.

Using these samples, the moisture and heat deterioration resistance and generation of adhesive substances on the surface were examined in the same manner as in Example 1.

The results are also listed in Table 1 below.

Comparative Example 1 First, 100 parts by weight of ether polyurethane as a polyurethane resin, 10 parts by weight of trichloroethyl phosphate as a halogen flame retardant, 5 parts by weight of antimony trioxide, and 6 parts by weight of epoxidized oleic acid were mixed. The resulting mixture was kneaded with a roll. Next, this kneaded material was press-molded to obtain a sheet-like material having a thickness of 1.1lII. Thereafter, the obtained sheet-like body was punched out to produce a dumbbell-shaped sample.

Using the obtained sample, the moisture and heat deterioration resistance and generation of adhesive substances on the surface were examined in the same manner as in Example 1.

The results are also listed in Table 1 below.

Comparative examples 2 to 5 The components shown in Table 1 below were mixed in the amounts shown in the same table.

Using the obtained mixture, Comparative Example 2 was prepared in the same manner as Comparative Example 1.
~5 samples were prepared.

Using these samples, the moisture and heat deterioration resistance and generation of adhesive substances on the surface were examined in the same manner as in Example 1.

The results are also listed in Table 1 below.

As is clear from Table 1, the flame-retardant polyurethane resin compositions (Examples) to 7 of the present invention exhibited high characteristic retention after an accelerated test at a temperature of 80°C and a humidity of 95% RH for 240 hours. Indicated. That is, high tensile elongation and tensile strength were exhibited even after the accelerated test. Furthermore, no adhesive substance was observed on the surface.

On the other hand, conventional flame-retardant polyurethane resin compositions (Comparative Examples 1 to 5) that do not contain montan wax had extremely low characteristic retention rates after the accelerated test. Moreover,
This composition generated a sticky substance on the surface.

[Effects of the Invention] As explained above, the flame-retardant polyurethane resin composition according to the present invention has excellent water resistance, and also has excellent properties such as flame retardancy, mechanical strength, and flexibility. It is something.

Claims (1)

[Claims] For 100 parts by weight of polyurethane resin, 1 to 35 parts by weight of a halogen flame retardant, 3 to 16 parts by weight of antimony trioxide, and 0.1 part of a compound having one epoxy group in one molecule at a position other than the end of the molecule. 15 parts by weight of a flame-retardant polyurethane resin composition and 0.1 to 6 parts by weight of montan wax.