JPS5937288B2 - Method for manufacturing polyurethane elastomer - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel polyurethane resin with excellent durability, and more specifically, it overcomes the drawbacks of conventional polyurethane resins such as light deterioration resistance, discoloration resistance, hydrolysis resistance, and heat deterioration resistance. It is an object of the present invention to provide a method for producing polyurethane resins with improved durability.

Conventionally, polyurethane resins have been known to use polyester polyols, polyether polyols, and a combination of both as the polyol component, but polyester polyurethanes are generally Although polyether polyurethane has improved hydrolysis resistance, its heat deterioration resistance is extremely poor.

In addition, polyester-polyether polyurethane is
It has an intermediate durability between polyester-based and polyether-based, and cannot be said to be sufficient in either case.

Furthermore, polycarbonate polyols are known which use polycarbonate polyols as polyols, but although these have excellent hydrolysis resistance, their light deterioration resistance is not satisfactory. The inventor of the present invention solved the above-mentioned drawbacks of the prior art and, as a result of intensive research to obtain a polyurethane resin with various durability improvements at the same time, by using a new polyester polyol as the polyol component of the polyurethane resin, The present invention was completed based on the finding that a polyurethane resin with excellent durability can be obtained that solves various drawbacks of conventional polyurethane resins at the same time.

That is, the present invention provides a method for producing polyurethane by reacting a polyol, a polyisocyanate, and, if necessary, a chain extender.
This is a method for producing a polyurethane elastomer with excellent durability, characterized by using a polyester diol consisting of decanedicarboxylic acid and polycarbonate diol.

To explain the present invention in more detail, the polyester diol used as the polyol in the present invention uses 1.10 decanedicarboxylic acid as the main component of the acid component, polycarbonate diol as the main component of the polyol component, and contains both components. The ratio of carboxyl group to hydroxyl group is O
H/C00H=1.0-2.0) preferably 1.1-1
．． It can be obtained by esterification in a conventional manner at a ratio of 6 to 6. 1,10-decanedicarboxylic acid itself is a known material, and it is preferable to use this dicarboxylic acid alone, but other known polyhydric carboxylic acids used in the production of polyurethane may be used in combination in a certain proportion. You can also do that.

When other polycarboxylic acids are used in combination, it is desirable that the proportion be less than about 0.3 molar per 1 molar proportion of 1,10-decanedicarboxylic acid, and if used in a proportion above this range, the degree of the effect of the present invention will be reduced. This will result in a decline. Polycarbonate diol used as a polyol component is itself a known material, and is obtained by combining a conventionally known polyhydric alcohol with phosgene, chloroformate, dialkyl carbonate, or diallyl carbonate, and is available in various molecular weights. ing. Particularly preferred as such polycarbonate diol are those using 1,6-hexanediol, 1,4-butanediol, 1,3-butanediol, neopentyl glycol or 1,5-pentanediol as the polyhydric alcohol. It has a molecular weight of about 200 to 100,001 and a hydroxyl value of about 10 to 560. Such polycarbonate diols may be used alone, but
It is also possible to use it in combination with polyhydric alcohols such as those mentioned above. For the purpose of the present invention, the polyester diol consisting of an acid component and an alcohol component as described above preferably has a molecular weight of about 600 to 220,000 and a hydroxyl value of about 5 to 190, and such a polycarbonate diol can be used alone. Although it is preferable to use these polyols, it is also possible to use them in combination with other polyester polyols, polyether polyols or polyester-polyether polyols known for the production of polyurethanes. When used together, the other polyol is polycarbonate diol 10
It is desirable that the amount is about 30 parts by weight or less per 0 parts by weight,
If it exceeds this range, the desired effect cannot be obtained. The organic diisocyanates to be reacted with the specific polyester diols mentioned above include tolylene diisocyanate (TDI),
4,4'-diphenylmethane diisocyanate (MDI
), xylene diisocyanate (XDI), 1,5-naphthylene diisocyanate (NDI), hexamethylene diisocyanate (HD), water-added TDI, water-added MDI, isoborone diisocyanate (IPDI), diisocyanate (LDI), isopropylidene Screw(
4-cyclohexyl isocyanate (IPCI) and other known diisocyanates can be used.

From the viewpoint of light resistance of the resulting polyurethane, it is preferable to use aliphatic or alicyclic diisocyanates, and from the viewpoint of cost and physical properties, water-added MDI. IPD
Particularly preferred are I and the like. When producing polyurethane from polycarbonate diol and diisocyanate as described above, appropriate amounts of chain extenders known in the prior art such as polyhydric alcohols, aliphatic polyamines, alicyclic polyamines, aromatic polyamines, etc. as described above are used. It is preferable.

The polyurethane according to the present invention can be prepared by using the above specific polyester diol and the above diisocyanate, preferably in combination with a suitable chain extender, at about 0 to 150°C for about 2 to 10 hours in the presence or absence of a suitable solvent. Obtained by reaction.

The polyurethane resin of the present invention obtained as described above has a molecular weight of about 10,000 to 500,000, and has better hydrolysis resistance, heat deterioration resistance, light deterioration resistance, etc. compared to conventionally known polyurethane resins. It has been greatly improved and is useful as a raw material for synthetic leather, a raw material for paints, a raw material for various molded products, various engineering resins, and other applications that cannot be used with conventional polyurethane resins. Next, the present invention will be specifically explained with reference to Examples.

Note that parts and percentages in the text are based on weight. Example 1 354 parts of diethyl carbonate and 708 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 501 parts.
The ethanol remaining as 1Hg was sufficiently distilled off, and 78
6 parts of polycarbonate diol were obtained.

The hydroxyl value of this diol is about 427. In this diol, 236 parts of 1,6-hexanediol and 1,10-
Add 920 parts of decanedicarboxylic acid, about 200 to 220 parts
The reaction was carried out at ℃ for 8 hours, and the reaction was carried out under reduced pressure of 30 to 50 muHg to finally obtain 1750 parts of polycarbonate polyester diol. The molecular weight of this diol is approximately 180
6, and its hydroxyl value was about 62. 150 parts of this diol, 5 parts of 1,6-hexanediol, 20 parts of isophoronediamine, and 85 parts of water-added MDl were added to approximately 80 parts of
After reacting at ~120°C for about 8 hours, isopropanol/
Dissolved in 607 parts of toluene (1:1) mixed solvent, concentration 3
The polyurethane resin of the present invention with a viscosity of 860 poise at 0% (
A solution with an average molecular weight of 13,200 was obtained. Example 2 1284 parts of diphenyl carbonate, 270 parts of 1,4-butanediol and 708 parts of 1,6-hexanediol were reacted at 150 to 210°C for 18 hours, resulting in a reaction of 30 to 50 parts.
The pressure was reduced to Hg, and phenol was sufficiently removed to obtain 1134 parts of polycarbonate diol.

460 parts of 1,10-decanedicarboxylic acid was added to this, and the mixture was reacted at 200 to 220°C for 8 hours.
The pressure was reduced to mHg to finally obtain 1500 parts of polycarbonate polyester diol. The molecular weight of this product was about 1,555, and the hydroxyl value was 72. 150 parts of this diol, 5 parts of 1,4-butanediol, I
79.3 parts of PDl, 23.4 parts of water-added MDI and IP
33.7 parts of DA was reacted and then dissolved in dimethylformamide to make the concentration 30%, and the polyurethane resin of the present invention having a viscosity of 660 poise (average molecular weight 1160
00) solution was obtained. Example 3 Polycarbonate diol 1310 obtained in Example 1
A polycarbonate polyester diol having a molecular weight of 2,036 and a hydroxyl value of **55 was obtained in the same manner as in Example 1 using 690 parts of 1,10-decanedicarboxylic acid and 146 parts of adipic acid.

The polyurethane resin of the present invention (
A solution with an average molecular weight of 215,000 was obtained.

Performance comparison test The performance of the polyurethane resin of the present invention obtained in the above example and the conventional polyurethane resin was investigated.
As shown in the table, the polyurethane resin of the present invention was significantly superior in hydrolysis resistance, heat deterioration resistance, and light deterioration resistance compared to conventional polyurethane resins.

The test pieces were prepared by coating each polyurethane resin solution on a glass plate so that the dry thickness was approximately 40 to 50 microns, drying at 70°C for 3 minutes and at 120°C for 10 minutes. After being left at room temperature for one day, it was subjected to each test.

Reference Examples 1 to 3 in Table 1 below are conventionally known polyurethane resins, Reference Example 1 is a polyurethane resin whose polyol component is a conventional polycarbonate polyol, and Reference Example 2 is a polyurethane resin whose polyol component is a conventional polyester polyol. Reference Example 3 is a polyurethane resin whose polyol component is a conventional polyether polyol.

In addition, the hydrolysis resistance was determined by the di-angle test (exposure condition 70
℃, relative humidity 95%), heat resistance was determined by continuous exposure at 120°C with gear open, and light deterioration resistance was determined by continuous irradiation at 63°C with a sash yarn fade meter black panel temperature.

Claims (1)

[Claims] 1. A method for producing polyurethane by reacting a polyol, a polyisocyanate, and optionally a chain extender, characterized in that a polyester diol consisting of 1,10-decanedicarboxylic acid and a polycarbonate diol is used as the polyol. A method for producing polyurethane elastomer with excellent properties.