JPS5811898B2 - polyurethane foam - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to improving the antistatic properties of polyurethane resins.

Polyurethane resin has mechanical strength, chemical resistance, weather resistance,
It has excellent water resistance, and taking advantage of this feature, it has a wide range of applications such as footwear, interior materials for automobiles and other vehicles, furniture, insulation materials, cushions, fibers, rollers, urethane rubber, and artificial wood. Its uses are expanding.

Due to these wide range of uses, many problems have arisen due to the generation of static electricity, and there is a need for ways to prevent this, but at present there are no antistatic agents for polyurethane resins. be.

As a result of intensive research into this problem, the present inventors discovered that the generation of static electricity can be prevented by adding a dicarboxylic acid diester described below.

The dicarboxylic acid diester added to the polyurethane resin of the present invention has the following general formula: R10℃R20
←0CR3COSOOR4HinokiOR6 However, R1 and R5 are C1 to CtS alkyl groups.

R2O-2R40- is ethylene oxide or propylene oxide or a mixture of both.

R3 is a saturated or unsaturated dicarboxylic acid residue.

n and m are integers from 0 to 50.

More specifically, the saturated dicarboxylic acids used herein include oxalic acid, malonic acid, succinic acid, gludaric acid, adipic acid, pimelic acid, superric acid, azelaic acid, sebacic acid, and acid anhydrides thereof.

Further, as the unsaturated dicarboxylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, and acid anhydrides thereof, etc. are used.

The alcohol residues represented by R10- and R60- have C
Alcohols of 1 to Ct8 can be used here.

That is, alcohols such as methanol, ethanol, propatool, butanol, octatool, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol, etc., either as they are, or with ethylene oxide or propylene oxide added alone; Alternatively, a mixture of both can be used.

The reaction method for producing the dicarboxylic acid diester is based on a commonly used esterification reaction.

That is, predetermined amounts of dicarboxylic acid and alcohol (including alkylene oxide addition polymers) are heated at 130 to 160°C.
The dehydration reaction is carried out by heating to .

In this case, the reaction will proceed even if no catalyst is added, but the reaction will be accelerated if a catalyst is added.

Examples of catalysts include acidic catalysts usually used in esterification reactions,
That is, sulfuric acid, hydrochloric acid, phosphoric acid, para-toluenesulfonic acid, etc. can be used.

Dicarboxylic acid diesters can also be obtained by transesterification.

The diester dicarboxylate thus obtained is used to foam polyurethane resins, such as urethane elastomers, soft urethane foams, and hard urethane foams (
1) Mix in advance with either polyol or polyisocyanate.

(2) Handle and add in the same way as conventional raw materials.

Either of these methods can be used.

The polyurethane resin to which dicarboxylic acid diester is added as described above has no change in foaming time or foam properties compared to one without the addition, and can be used without any changes in conditions compared to conventional foam production. I can do it.

When measuring the surface resistance of the polyurethane resin after molding, the polyurethane resin to which the dicarboxylic acid diester of the present invention is added has an electrical resistance of 108 to 1010 Ωcm-1, while that of the polyurethane resin without addition is 1012 to 1013 Ωcm.
It was found that the electrical resistance was lower than that of -1, and that the antistatic properties were excellent.

This will be explained below using examples.

Example 1 Dimethyl itaconate 395 parts Octyl alcohol ethylene 4114815 mole adduct 790 parts Para-toluenesulfonic acid 5.9 parts Hydroquinone 0.6 parts The above mixture was added to 1
Heat and stir at 40 to 150° C. while blowing N2 gas, and react for 5 hours.

In the infrared absorption spectrum at the end of the reaction, the absorption of hydroxyl groups at 2.85 microns disappeared.

After this time, excess dimethyl itaconate is removed under reduced pressure to obtain the ester.

Commercially available prepolymer for elastomer (Adiprene L-1
00) Mix 100 parts of itaconic acid diester synthesized above uniformly, add 12 parts of 4゜4'-methylene-bischloroaniline as a hardening agent, and add 110 parts of itaconic acid diester synthesized above while casting.
Aging for 1 hour at ℃ and demolding.

The elastomer sheet obtained in this manner has a surface electrical resistance value of 101 without addition of itaconic acid diester.
3 Ω/cm or more, whereas the added sheet had 2 Ω/cm or more.
×1010 Ω/cm, and the antistatic ability is significantly improved.

Example 2 Adipic acid 146 parts Octyl alcohol ethylene 4111110 mole adduct 1140 parts Para-toluenesulfonic acid 6 parts The above mixture was heated and stirred at 150 to 160° C. while blowing N2 gas, and reacted for 6 hours.

100 parts of general polyol (Mw: 4000), 2 parts of the above diester, 3 parts of water, 0.65 parts of catalyst (33LV),
Add 1 part of morpholine and stir evenly.

and MDI50/TDI50 mixed isocyanate 4
Add 2 parts and foam.

The urethane foam obtained in this way has an electrical resistance value of 1013 Ω/cy without adding the diester.
n or more, whereas the added form is 3×10
10Ω/cm, and the antistatic ability is significantly improved.

Example 3 Succinic anhydride 96 parts Lauryl alcohol Ethylene 998 parts Oxide 7 mole adduct para-toluenesulfone e 2. Part s The above mixture was heated and stirred at 110 to 160° C. while blowing nitrogen gas, and the reaction was carried out for 4.5 hours to obtain an ester with an acid value of 1.2.

250 parts of TDI and 0.1 part of water are added to 100 parts of polyoxypropylene glyceryl ether (average molecular weight 450) and heated to produce a prepolymer.

0.5 parts of silicone oil to 100 parts of this prepolymer,
30 parts of polyoxypropylene glyceryl ether (Mw450) containing 1.0 part of diethylethanolamine, 2.0 parts of water, and 1.5 parts of the above ester were added, stirred vigorously, poured into a mold, and foamed. 2 at ~80℃
Perform time curing treatment.

When the electrical resistance value of the obtained foam was measured, it was 4×101
0 Ω/cm, and as a result of making an ester-free foam with the above-mentioned formulation and measuring the electrical resistance value, it was 101
It is 3Ω/cm or more, and the antistatic ability is significantly improved by adding the ester.

Claims (1)

[Claims] 1 General formula % Formula % where R1 and R5 are C1 to C18 alkyl groups. -0R2- and -0R4- are ethylene oxide or propylene oxide, or a mixture of both. R3 is a saturated or unsaturated dicarboxylic acid residue. m and n are integers from 0 to 50. Polyurethane resin modifier 6, characterized in that it improves the antistatic properties of polyurethane resin by adding dicarboxylic acid ester represented by