URETHANE ACRYLATES BASED ON 2,4,8,10-TETRAOXOSPIRO[5.5]-UNDECANE-3,9-DIALKANOLS

Abstract

Disclosed is a novel urethane acrylate being a reaction product of a raw material composition comprising at least (A) a diol component, (B) a component having acrylic unsaturation and (C) an isocyanate component. Said component (A) comprises at least one alkoxylated 2,4,8,10-tetraoxaspiro[5.5]undecane-3,9-dialkanol, component (B) comprises at least one hydroxyalkyl acrylate, hydroxyalkyl methacrylate and/or hydroxyalkyl methylacrylate, and/or comprises acrylic acid, methacrylic acid and/or a methylacrylic acid and/or a corresponding alkyl ester of a said acrylic acid, and said component (C) comprises at least one di or polyisocyanate or a derivative thereof.

Claims

1. A urethane acrylate being a reaction product of a raw material composition comprising at least (A) a diol component, (B) a component having acrylic unsaturation and (C) an isocyanate component characterised in, that said component (A) comprises at least one alkoxylated 2,4,8,10-tetraoxaspiro[5.5]undecane-3,9-dialkanol of formula ##STR00003## wherein each substituent R individually is a linear or branched C.sub.1-C.sub.8 alkyl group and m, n, p and q individually are integers each being at least 1, that said acid component (B) comprises at least one hydroxyalkyl acrylate, hydroxyalkyl methacrylate and/or hydroxyalkyl methylacrylate, and/or comprises acrylic acid, methacrylic acid and/or a methylacrylic acid and/or a corresponding alkyl ester of a said acrylic acid, and that said component (C) comprises at least one di or polyisocyanate and/or a derivative thereof.

2. The urethane acrylate according to claim 1 characterised in, that said hydroxyalkyl is hydroxy-C.sub.1-C.sub.12-alkyl.

3. The urethane acrylate according to claim 1 characterised in, that said component (B) comprises hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, trimethylolpropane di(meth)acrylate and/or pentaerythritol tri(meth)acrylate.

4. The urethane acrylate according to any of the claim 1 characterised in, that m and p independently are integers each being between 1 and 6.

5. The urethane acrylate according to any of the claim 1 characterised in, that m and p independently are integers each being between 1 and 4.

6. The urethane acrylate according to any of the claim 1 characterised in, that n and q independently are integers each being between 1 and 10.

7. The urethane acrylate according to any of the claim 1 characterised in, that n and q independently are integers each being between 1 and 6.

8. The urethane acrylate according to any of the claim 1 characterised in, that each substituent R is an alkyl group of formula ##STR00004##

9. The urethane acrylate according to any of the claim 1 characterised in, that said alkoxylated 2,4,8,10-tetraoxaspiro[5.5]undecane-3,9-dialkanol is an alkoxylated 2,4,8,10-tetraoxaspiro[5.5]undecane-3,9-diethanol.

10. The acrylic compound according to any of the claim 1 characterised in, that said alkoxylated is ethoxylated, propoxylated and/or butoxylated.

11. The urethane acrylate according to any of the claim 1 characterised in, that said component (A) comprises 50-100% by weight of said alkoxylated 2,4,8,10-tetraoxaspiro[5.5]undecane-3,9-dialkanol.

12. The urethane acrylate according to any of the claim 1 characterised in, that said component (A) comprises 70-100% by weight of said alkoxylated 2,4,8,10-tetraoxaspiro[5.5]undecane-3,9-dialkanol.

13. The urethane acrylate according to any of the claim 1 characterised in, that said component (A) comprises 80-100% by weight of said alkoxylated 2,4,8,10-tetraoxaspiro[5.5]undecane-3,9-dialkanol.

14. The urethane acrylate according to claim 1 characterised in, that said alkoxylated 2,4,8,10-tetraoxaspiro[5.5]undecane-3,9-diethanol is an ethoxylated and/or propoxylated 2,4,8,10-tetraoxaspiro[5.5]undecane-3,9-diethanol.

15. The urethane acrylate according to any of the claim 1 characterised in, that said component (B) comprises 50-100% by weight of said hydroxyalkyl acrylate, hydroxyalkyl methacrylate and/or hydroxyalkyl methylacrylate.

16. The urethane acrylate according to any of the claim 1 characterised in, that said component (B) comprises 50-100% by weight of said acrylic acid, methacrylic acid and/or a methylacrylic acid and/or an alkyl ester of a said acrylic acid.

17. The urethane acrylate according to any of the claim 1 characterised in, that said di or polyisocyanate is toluene diisocyanate, diphenyl methane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, tetramethylxylene diisocyanate, dicyclohexyl methane diisocyanate, furan diisocyanate, tetrahydrofuran diisocyanate, cyclohexylene diisocyanate, xylene diisocyanate, naphthalene diisocyanate, phenylene diisocyanate, nonane triisocyanate and/or triphenyl methane triisocyanate.

18. The urethane acrylate according to any of the claim 1 characterised in, that said raw material composition additionally comprises at least one carboxylic acid.

19. The urethane acrylate according to claim 18 characterised in, that said carboxylic acid is octanoic acid, 2-ethylhexanoic acid, 2-propylheptanoic acid, cecanoic acid and/or trimethylhexanoic acid.

20. The urethane acrylate according to any of the claim 1 characterised in, that said component (A) comprises an ethoxylated 2,4,8,10-tetraoxaspiro[5.5]undecane-3,9-diethanol having an average of 3-6 ethoxy units/hydroxyl group, that said component (B) comprises hydroxyethyl acrylate and that said component (C) comprises isophorone diisocyanate.

Description

EXAMPLE 1

[0016] An adduct between isophorone diisocyanate and hydroxyethyl acrylate was produced for use in productions of urethane acrylates as disclosed in Examples 2 and 3 (comparative).

[0017] 175.0 parts by weight of isophorone diisocyanate and 0.6 parts by weight of methoxy phenol, as inhibitor, were charged to a reaction vessel, equipped with a heating device, temperature control, stirrer, air inlet and a cooler. 86.8 parts by weight of hydroxyethyl acrylate was successively during 10 minutes charged and 0.03 part by weight of dibutyltinlaurate as catalyst was subsequently charged to the reaction mixture. The temperature was now slowly raised to 60-70° C. and the reaction was allowed to continue until the theoretical remaining NCO value was reached. Yielded reaction product was finally cooled to room temperature.

EXAMPLE 2

[0018] 54.5 parts by weight of an ethoxylated 2,4,8,10-tetraoxaspiro[5.5]undecane-3,9-diethanol, having an average of 4-5 ethylene oxide units/hydroxyl group (pentacrythritol spiroglycol ethoxylate, Perstorp Specialty Chemicals AB), 0.2 parts by weight of methoxy phenol as inhibitor and 133.0 parts by weight of toluene as azeotropic solvent were charged to a reaction vessel, equipped with a heating device, temperature control, stirrer, air inlet and reflux. 100.0 parts by weight of the adduct yielded in Example 1 was now slowly charged to the reaction mixture followed by charging of 0.03 parts by weight of dibutyltinlaurate as catalyst. The temperature was rapidly raised to 65° C. and maintained until the NCO value was close to 0. Toluene was now evaporated and remaining reaction product was cooled to room temperature. Properties measured on obtained product are given in Table 1.

EXAMPLE 3 (COMPARATIVE)

[0019] Example 2 was repeated with the difference that 52.4 parts by weight of a bisphenol A ethoxylate having an average of 4 ethoxy units/phenolic hydroxyl group (Sigma Aldrich Co) was charged instead of 54.5 parts by weight of the ethoxylated 2,4,8,10-tetraoxaspiro-[5.5]undecane-3,9-diethanol. Properties measured on obtained product are given in Table 1.

EXAMPLE 4

[0020] The products yielded in Examples 2 and 3 (comparative) were, after addition of 1.0 part by weight of Irgacure 500 (Photoinitiator, Ciba Specialty Chemicals Inc.), coated on glass and steel panels at a dry film thickness of 40 μm and cured.

[0021] The coated panels were first placed in an oven for 30 minutes at 50° C., cooled to room temperature and subsequently UV cured. UV curing was performed by means of a UV-lamp of 80 W/cm.sup.2 and at a belt speed of 20 m/min. The lacquers were allowed to pass the UV-lamp 4 times. The samples were after curing conditioned for 24 hours at 23±2° C. and 50±5% relative humidity followed by measuring of film hardness, flexibility and gloss.

[0022] Recorded Results:

TABLE-US-00001 Example 2 Example 3 Hardness, König secs. 214 200 Erichsen flexibility, mm 0.4 2.6 Gloss at 60° 89 94

TABLE-US-00002 TABLE 2 Example 2 Example 3 Hydroxyl value, mg KOH/g 4   5   Acid value, mg KOH/g 0.1 0.3 Molecular weight Mw, g/mol 2 200    2 400    Acrylic concentration IR  1.40  1.42 Polydispersity 1.4 1.4