JPH06256462A - Stabilized polyurethane - Google Patents

Abstract

PURPOSE:To obtain a polyurethane excelling in extraction resistance and volatilization resistance, not undergoing blooming or bleeding and improved in weather resistance. CONSTITUTION:This stabilized polyurethane contains groups of the formula (wherein R1 is hydrogen, methyl or ethyl; R2 is 2-4C alkylene, and (n) is 0-10) in the molecule.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a stabilized polyurethane, and more particularly to a modified polyurethane stabilized by the action of light by introducing a specific piperidine compound into a molecule.

[0002]

BACKGROUND OF THE INVENTION Polyurethane has excellent properties and is used in a wide variety of applications such as various molded products, artificial leather, fibers, paints and sealants. However, since polyurethane is inferior in weather resistance, its use outdoors is restricted. Therefore, it has been proposed to add a phenol-based antioxidant, a phosphite-based antioxidant, a benzophenone-based, a benzotriazole-based ultraviolet absorber, a piperidine compound, etc., either alone or in combination. When a stabilizer is used, it has drawbacks such as extraction by a solvent, volatilization during processing, and bleeding or blooming from a molded product.

In order to solve these drawbacks, for example,
JP-A-56-43478 and JP-A-59-102.
In 950, it is proposed to use a piperidine compound as a polyurethane end-stopping agent.
1294, JP-A-53-39395, JP-A-53-39396, and JP-A-56-15282.
No. 7, it is proposed to introduce a piperidine compound into the main chain of polyurethane, but the extractability, volatility,
Although the defects such as bloom and bleed have been solved, the weather resistance has not been sufficiently improved.

Accordingly, it is an object of the present invention to provide a polyurethane having excellent weather resistance, which is excellent in extraction resistance and volatility resistance and does not cause blooming or bleeding.

[0005]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies to achieve the above object, and as a result, by introducing a specific piperidine derivative into the molecule of polyurethane, extraction resistance and volatility resistance are improved. The inventors have found that the present invention is excellent and that the weather resistance is remarkably improved without causing blooming or bleeding, and has reached the present invention.

That is, the present invention is characterized in that the molecule contains a group represented by the following general formula (I) (the same as the general formula (I) of the above (chemical formula 1)). To provide a stabilized polyurethane.

[0007]

[Chemical 2]

Hereinafter, the stabilized polyurethane of the present invention will be described in detail.

The polyurethane of the present invention uses a polyether polyol and / or a polyester polyol having a hydroxyl group at the terminal and a polyisocyanate, and a piperidine compound represented by the following general formula (II) If necessary, a chain extender or the like may be added, and the compound can be produced by a conventional one-shot method, prepolymer method, pseudo-prepolymer method, or the like. The piperidine compound represented by (II) may be added at any stage of the reaction.

[0010]

[Chemical 3]

In the above general formulas (I) and (II), examples of the alkylene group represented by R ₂ include ethylene, 1, and
Examples of the lower alkyl group represented by R ₃ include groups such as 2-propylene, 1,3-propylene, 1,2-butylene and 1,4-butylene. Examples of the lower alkyl group represented by R ₃ include methyl, ethyl,
Examples include groups such as propyl and butyl.

Examples of the piperidine compound represented by the above general formula (II) used in the production of the polyurethane of the present invention include No. 1 to No. 7 of the following [Chemical formula 4] to [Chemical formula 10].
Compounds of are exemplified.

[0013]

[Chemical 4]

[0014]

[Chemical 5]

[0015]

[Chemical 6]

[0016]

[Chemical 7]

[0017]

[Chemical 8]

[0018]

[Chemical 9]

[0019]

[Chemical 10]

Examples of the above-mentioned polyether polyol used in the production of the polyurethane of the present invention include polyoxyethylene glycol, polyoxypropylene glycol, polyoxypropylene-polyoxyethylene glycol, polyoxybutylene glycol,
Examples thereof include polyoxypropylene triol and polyoxypropylene tetraol.

The polyester polyol used in the production of the polyurethane of the present invention is produced from a polybasic acid and a polyhydric alcohol, and examples of the polybasic acid include succinic acid, adipic acid, sebacic acid, maleic acid and phthalic acid. Acid, trimellitic acid, and the like. Examples of the polyhydric alcohol include elene glycol, propylene glycol,
Butanediol, pentanediol, hexanediol, diethylene glycol, trimethylolpropane,
Examples include trimethylolethane, glycerin, hexanetriol, and pentaerythritol.

Polycaprolactone glycol derived from poly-ε-caprolactone, poly (β-methyl-δ-valerolactone) and the like can also be used as the polyester polyol.

The polyisocyanates used in the production of the polyurethane of the present invention include 2,4-
Tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 3,3'-dimethyl-4,4'-biphenyldiamine, tolidine diisocyanate, xylylene diisocyanate , 1,5-naphthylene diisocyanate, isophorone diisocyanate, triphenylmethane diisocyanate, lysine diisocyanate, hexane methylene diisocyanate, dimerisocyanate isocyanate, phenylene diisocyanate, diphenyl ether diisocyanate, dianisidine diisocyanate, bis (isocyanatomethyl) cyclohexane, dicyclohexylmethane diisocyanate, etc. can give.

The chain extender usable in the production of the polyurethane of the present invention includes ethylene glycol, propylene glycol, 1,4-butanediol,
Neopentyl glycol, 1,6-hexanediol,
Diethylene glycol, triethylene glycol, 1,
4-Cyclohexanedimethanol, glycerin, trimethylolpropane, hexanetriol, 1,4-bis (β-hydroxyethoxy) benzene, polyhydric alcohol such as N, N′-bis (β-hydroxyethyl) aniline, hydrazine, ethylenediamine , Propylenediamine, menthanediamine, isophoronediamine, 4,4 '
-Diaminodicyclohexylmethane, 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane, p-
Phenylenediamine, m-phenylenediamine, tolylenediamine, naphthylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylthioether,
4,4'-diaminodiphenyl sulfone, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3,
Amines such as 3′-dichloro-4,4′-diaminodiphenylmethane and 1,6-hexamethylenediamine,
Amino alcohols such as monoethanolamine, diethanolamine, monopropanolamine, dipropanolamine and the like can be mentioned.

In producing the polyurethane of the present invention,
A solvent such as benzene, chlorobenzene, tetrahydrofuran or dimethylformamide can be used. The reaction temperature is appropriately selected from the range of 20 to 150 ° C.

In producing the polyurethane of the present invention, a tertiary amine such as triethylenediamine or an organometallic compound such as dilauryltin can be used as a reaction accelerator.

The content of the group represented by the general formula (I) in the polyurethane of the present invention is preferably 0.0001 to 0.5 mmol, more preferably 0.001 to 0.1, per 1 g of polyurethane. It is millimoles.

Various commonly used additives can be added to the polyurethane of the present invention. Examples of these additives include phenolic antioxidants, phosphite compounds, sulfur-containing compounds, ultraviolet absorbers, metal soaps, antistatic agents, flame retardants, foaming agents, thixotropic agents,
Examples include pigments and fillers. When used in polyurethane paints, lacquers, etc., cellulose derivatives such as cellulose nitrate, cellulose acetate-propionate and cellulose acetate-butyrate can be added.

These additives can be added during the production of the polyurethane or before the molding of the polyurethane.

[0030]

The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited by the following examples.

In the following examples, the compounds of Comparative-1 to Comparative-3 of the following [Chemical formula 11] to [Chemical formula 13] were used as comparative compounds.

[0032]

[Chemical 11]

[0033]

[Chemical 12]

[0034]

[Chemical 13]

Example 1 260 g (0.1 mol) of a polyester polyol having a molecular weight of 2600 and a hydroxyl value of 44 produced from adipic acid and 1,4-butanediol and 34.8 g (0.2 mol) of tolylene diisocyanate were added to nitrogen. 100 ° C under air flow
And reacted for 1.5 hours. Then, 8.1 g (0.095 mol) of 1,4-butanediol and a test compound Xg (0.01 mol) shown in the following [Table 1] were added and reacted at 100 ° C. for 1.5 hours.

After cooling, 300 g of dimethylformamide was added to make the product a viscous solution, and the solution was applied onto an aluminum foil and dried to form a dry film having a thickness of 0.5 mm, and tensile breaking strength (kg / cm ² ) And the elongation rate (%) were measured.
Further, the same test was conducted on a sample after the film was irradiated with high pressure mercury for 80 hours.

The results are shown in the following [Table 1].

[0038]

[Table 1]

Example 2 100 g (0.05 mol) of polytetramethylene glycol ether having a molecular weight of 2000 and 13.9 g (0.08 mol) of tolylene diisocyanate were reacted at 120 ° C. for 30 minutes. Then, 1,4-butanediol 2.25
g (0.025 mol) and the test compound Yg (0.005 mol) shown in the following [Table 2] were added and reacted at 100 ° C. for 1.5 hours.

The solution thus obtained was dry-spun by a conventional method to obtain a 40-denier elastic yarn. The elongation residual ratio (%) of the obtained elastic yarn after irradiation with a fade meter for 50 hours was measured. A similar test was conducted on elastic yarns extracted with carbon tetrachloride for 2 hours.

The results are shown in Table 2 below.

[0042]

[Table 2]

The following can be understood from the above embodiment. The polyurethane used in the production of the addition-type piperidine compound having no reactivity with the polyisocyanate component has poor weather resistance,
Easily extracted by solvent. Further, the polyurethane introduced with a group having a piperidyl group having reactivity with a polyisocyanate component other than the present invention has an improved extractability by a solvent, but its weather resistance is still inferior. On the other hand, the polyurethane introduced with the group having a piperidyl group of the present invention is not extracted with a solvent or the like and has excellent weather resistance.

[0044]

INDUSTRIAL APPLICABILITY The polyurethane having a specific piperidyl group of the present invention is excellent in extraction resistance and volatility resistance, and has improved weather resistance without bloom or bleeding.

Claims (1)

[Claims] 1. A stabilized polyurethane comprising a group represented by the following general formula (I) represented by the general formula (I) in the molecule. [Chemical 1]