UV and moisture-curable organopolysiloxane compositions, cured products therof, and method for making

• US 5,378,734 A
• Filed: 08/27/1993
• Issued: 01/03/1995
• Est. Priority Date: 09/07/1992
• Status: Expired due to Fees

• Current Assignee: Shin-Etsu Chemical Company Limited
• Original Assignee: Shin-Etsu Chemical Company Limited
• Inventors: Inoue, Yoshio
• Primary Examiner(s): Berman, Susan W.
• Application Number:
  US08/112,457
• Time in Patent Office: 494 Days
• Field of Search: 522/99, 522/11, 522/12, 522/39, 522/40, 522/43, 522/44, 522/45, 522/46, 522/68, 522/83, 528/26, 528/28, 528/32, 528/34, 528/35, 528/17, 526/279, 526/302
• US Class Current: 522/11
• CPC Class Codes: C08F 299/08 from polysiloxanes
• CPC Class Codes: C08G 77/388 containing nitrogen
• CPC Class Codes: C08K 5/0025 Crosslinking or vulcanising agents; including accelerators
• CPC Class Codes: C08L 83/08 containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen

Abstract

A UV and moisture-curable organopolysiloxane composition comprising (i) an organopolysiloxane terminated with a radical of formula (1): ##STR1## wherein R¹ is a hydrogen atom or monovalent hydrocarbon radical, each of R² and R³ is a divalent hydrocarbon radical which may contain a NH bond or ether bond, each of R⁴ and R⁵ is a monovalent hydrocarbon radical which may contain an ether bond, and a is equal to 0 or 1, (ii) a photo-polymerization initiator, and (iii) a curing catalyst. The composition readily cures either upon exposure to UV radiation or upon contact with moisture and from the surface to the deep interior within a short time, yielding cured products having satisfactory physical properties.

Claims

1. A UV and moisture-curable organopolysiloxane composition comprising

(i) an organopolysiloxane terminated with a radical of the formula (1):

##STR17## wherein R¹ is a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon radical, each of R² and R³ is a substituted or unsubstituted divalent hydrocarbon radical which may contain a NH bond or ether bond, each of R⁴ and R⁵ is a substituted or unsubstituted monovalent hydrocarbon radical which may contain an ether bond, and letter a is equal to 0 or 1,

(ii) a photo-polymerizable initiator, and

(iii) a curing catalyst.

2. A cured product obtained by curing the UV and moisture-curable organopolysiloxane composition of claim 1.

3. The UV and moisture-curable organopolysiloxane composition according to claim 1, wherein R¹ is a hydrogen atom or a methyl radical.

4. The UV and moisture-curable organopolysiloxane composition according to claim 1, wherein R² is an alkylene radical having 1 to 8 carbon atoms.

5. The UV and moisture-curable organopolysiloxane composition according to claim 1, wherein R³ is a C₁ -C₈ alkylene radical that may contain an NH or ether bond.

6. The UV and moisture-curable organopolysiloxane composition according to claim 1, wherein R⁴ and R⁵ are independently alkyl radicals having 1 to 4 carbon atoms or alkoxy radicals having 1 to 4 carbon atoms.

7. The UV and moisture-curable organopolysiloxane composition according to claim 1, wherein said photo-polymerization initiator is selected from the group consisting of acetophenone, propiophenone, benzophenone, xanthol, benzaldehyde, 4-methylacetophenone, 3-pentyl-acetophenone, 4-methoxyacetophenone, 3-bromo-acetophenone, 4-allylacetophenone, 3-methoxy-benzophenone, p-chlorobenzophenone, 4-dimethoxybenzophenone, 4-chloro-4-benzylbenzophenone, 3-chloroxanthol, benzoin, benzoin methyl ether, benzoin butyl ether, bis(4-dimethylaminophenyl)-ketone, benzylmethoxyketal, diethylacetophenone, 2,2-dimethoxy-2-phenylacetophenone, and diethoxyacetophenone.

8. The UV and moisture-curable organopolysiloxane composition according to claim 1, wherein the content of said photo-polymerization initiator is 0.01 to 5 parts by weight per 100 parts by weight of said organopolysiloxane of formula (1).

9. The UV and moisture-curable organopolysiloxane composition according to claim 1, wherein said curing catalyst allows said composition to cure with moisture.

10. The UV and moisture-curable organopolysiloxane composition according to claim 9, wherein said curing catalyst is selected from the group consisting of tin naphthenate, tin caprylate, tin oleate, dibutyltin diacetate, dibutyltin dioctotate, dibutyltin dilaurate, dibutyltin dioleate, diphenyltin diacetate, dibutyltin oxide, dibutyltin dimethoxide, dibutylbis(triethoxysiloxy)tin, dibutyltin benzylmaleate, tetraethoxytitanium, tetraisopropoxytitanium, tetra-n-butoxytitanium, tetrakis(2-ethyl-hexosy)titanium, dipropoxybis(acetylacetonato)-titanium, and titanium isopropoxyoctylene glycol.

11. The UV and moisture-curable organopolysiloxane composition according to claim 1, wherein the content of said curing catalyst is from 0.5 to 3 parts by weight per 100 parts by weight of said organopolysiloxane of formula (1).

12. A method for preparing a UV and moisture-curable organopolysiloxane composition comprising the steps of:

reacting (A) an organopolysiloxane terminated with a silanol radical with (B) an aminoalkylalkoxysilane of the formula (2);

##STR18## wherein R³ is a substituted or unsubstituted divalent hydrocarbon radical which may contain a NH bond or ether bond, each of R⁴ and R⁵ is a substituted or unsubstituted monovalent hydrocarbon radical which may contain an ether bond, and letter a is equal to 0 or 1,

such that the molar ratio of alkoxy radical in component (B) to silanol radical in component (A) may be at least 1, to thereby form an organopolysiloxane terminated with an aminoalkyl radical of the formula (3);

##STR19## wherein R³, R⁴, and R⁵ and a are defined above and a hydrolyzable alkoxy radical;

reacting the organopolysiloxane terminated with an aminoalkyl radical with (C) a compound of the formula (4);

##STR20## wherein R¹ is a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon radical, and R² is a substituted or unsubstituted divalent hydrocarbon radical which may contain a NH bond or ether bond,

such that the molar ratio of amino radical in the radical of formula (3) to NCO radical in component (C) may be at least 0.9, to thereby form an organopolysiloxane terminated with a radical of the formula (1);

##STR21## wherein R¹, R², R³, R⁴, R⁵, and a are defined above; and

mixing said organopolysiloxane terminated with a radical of formula (1) with a photo-polymerization initiator and a curing catalyst.

13. The method for preparing a UV and moisture-curable organopolysiloxane composition according to claim 12, wherein said organopolysiloxane terminated with a silanol radical is of the formula (5) ##STR22## wherein R⁶ and R⁷ are independently substituted or unsubstituted monovalent hydrocarbon radicals having 1 to 8 carbon atoms, and letter m is an integer of at least 5.

14. The method for preparing a UV and moisture-curable organopolysiloxane composition according to claim 13, wherein each of R⁶ and R⁷ is selected from the group consisting of lower alkyl radical, alkenyl radical and aryl radical, wherein some or all of the hydrogen atoms attached to the carbon atoms may be replaced by halogen atoms or cyano radicals, and letter m is an integer from 10 to 1000.

15. The method for preparing a UV and moisture-curable organopolysiloxane composition according to claim 12, wherein said aminoalkylalkoxysilane is selected from the group consisting of NH₂ CH₂ Si(OMe)₃, NH₂ C₃ H₆ Si(OMe)₃, NH₂ C₂ H₄ NHC₃ H₆ Si(OMe)₃, NH₂ C₂ H₄ NHCH₂ C₆ H₄ Si(OMe)₃, NH₂ C₂ H₄ OC₃ H₆ Si(OMe)₃, NH₂ CH₂ SiMe(OMe)₃, NH₂ C₃ H₆ SiMe(OMe)₂, NH₂ C₂ H₄ NHC₃ H₆ SiMe(OMe)₂, NH₂ C₂ H₄ NHCH₂ C₆ H₄ SiMe(OMe)₂, and NH₂ C₂ H₄ OC₃ H₆ SiMe(OMe)₂, wherein Me is a methyl group.

16. The method for preparing a UV and moisture-curable organopolysiloxane composition according to claim 12, wherein the molar ratio of alkoxy radical in component (B) to silanol radical in component (A) is from 1.5 to 10.

17. The method for preparing a UV and moisture-curable organopolysiloxane composition according to claim 12, wherein the molar ratio of alkoxy radical in component (B) to silanol radical in component (A) is from 2 to 4.

18. The method for preparing a UV and moisture-curable organopolysiloxane composition according to claim 12, wherein said compound of formula (4) is an acrylic compound having an isocyanato radical or a methacrylic compound having an isocyanato radical.

19. The method for preparing a UV and moisture-curable organopolysiloxane composition according to claim 12, wherein the molar ratio of amino radical in the radical of formula (3) to NCO radical in component (C) is from 0.95 to 1.05.