Radical-polymerizable resin composition, curing method thereof, method of producing same, use of radical-polymerizable resin composition, and use method of thereof

Patent metadata

Field	Value
Publication number	US-9969836-B2
Application number	US-201615543284-A
Country	US
Kind code	B2
Filing date	Apr 19, 2016
Priority date	Apr 21, 2015
Publication date	May 15, 2018
Grant date	May 15, 2018

Abstract

A radical-polymerizable resin composition comprising one or more metal-containing compounds (A) selected from a metal soap (A1) and a β-diketone skeleton-containing metal complex (A2); one or more thiol compounds (B) selected from a secondary thiol compound (B1) and a tertiary thiol compound (B2); and a radical-polymerizable compound (C) can stably cure under a dry condition, in water and in seawater and further on a wet substrate. The radical-polymerizable resin composition is useful as a repairing material for inorganic structure, a radical-polymerizable coating composition, a concrete spall preventing curable material, a reinforcing fiber-containing composite material, etc.

First claim

The invention claimed is:

1. A radical-polymerizable resin composition comprising one or more metal-containing compounds (A) selected from a metal soap (A1) and a β-diketone skeleton-containing metal complex (A2); one or more thiol compounds (B) selected from a secondary thiol compound (B1) and a tertiary thiol compound (B2); and a radical-polymerizable compound (C),
wherein a long-chain fatty acid constituting the metal soap (A1) is a linear or cyclic saturated fatty acid having 6 to 16 carbon atoms or an unsaturated fatty acid having 6 to 16 carbon atoms.

2. The radical-polymerizable resin composition of claim 1 , wherein the thiol compound (B) comprises at least one structure represented by formula (Q-1) and comprises two or more mercapto groups bonding to a secondary or tertiary carbon atom in the molecule including the mercapto group in the structure represented by formula (Q-1):

wherein R 1 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aromatic group having 6 to 18 carbon atoms; R 2 represents an alkyl group having 1 to 10 carbon atoms or an aromatic group having 6 to 18 carbon atoms; * bonds to an organic group; and a represents an integer of 0 to 2.

3. The radical-polymerizable resin composition of claim 2 , wherein the thiol compound (B) comprising at least one ester structure represented by formula (Q-1) is a compound derived from a mercapto group-containing carboxylic acid represented by formula (S) and a polyhydric alcohol:

wherein R′, R 2 and a are as defined in formula (Q-1).

4. The radical-polymerizable resin composition of claim 2 , wherein R 1 represents a hydrogen atom and the thiol compound (B) is a compound comprising 2 or more mercapto groups bonding to a secondary carbon atom in the molecule.

5. The radical-polymerizable resin composition of claim 1 , wherein the total amount of the thiol compound (B) is 0.01 to 10 parts by mass to 100 parts by mass of the radical-polymerizable compound (C).

6. The radical-polymerizable resin composition of claim 1 , wherein the molar ratio of the thiol compound (B) to the metal component in the metal-containing compound (A), (B)/(A), is 0.1 to 15.

7. The radical-polymerizable resin composition of claim 1 , wherein the radical-polymerizable resin composition comprises a radical polymerization initiator (D).

8. The radical-polymerizable resin composition of claim 7 , wherein the radical polymerization initiator (D) is a photoradical polymerization initiator.

9. The radical-polymerizable resin composition of claim 1 , wherein the metal soap (A1) is zirconium octylate, manganese octylate, cobalt octylate, or cobalt naphthenate.

10. The radical-polymerizable resin composition of claim 1 , wherein the radical-polymerizable compound (C) is one or more selected from a vinyl ester resin, an unsaturated polyester resin, a mixture of a vinyl ester resin and a radical-polymerizable unsaturated monomer, and a mixture of an unsaturated polyester resin and a radical-polymerizable unsaturated monomer.

11. The radical-polymerizable resin composition of claim 10 , wherein the radical-polymerizable compound (C) is one or more selected from a mixture of a vinyl ester resin and a radical-polymerizable unsaturated monomer, and a mixture of an unsaturated polyester resin and a radical-polymerizable unsaturated monomer, and wherein the radical-polymerizable unsaturated monomer is styrene and a styrene content in the radical-polymerizable compound (C) is 20% by mass or less.

12. A primer comprising the radical-polymerizable resin composition of claim 1 .

13. A repairing material for inorganic structure comprising the radical-polymerizable resin composition of claim 1 .

14. The repairing material for inorganic structure of claim 13 , wherein the repairing material for inorganic structure comprises a filler (F).

15. The repairing material for inorganic structure of claim 13 , wherein the repairing material for inorganic structure is a section repairing material, a crack injection material, or a water sealant.

16. The repairing material for inorganic structure of claim 13 , wherein a content of the radical-polymerizable compound (C) in the radical-polymerizable resin composition is 10 to 99.9% by mass.

17. The radical-polymerizable resin composition of claim 1 , wherein the metal-containing compound (A) is a metal soap (A1).

18. A radical-polymerizable coating composition comprising the radical-polymerizable resin composition of claim 17 .

19. The radical-polymerizable coating composition of claim 18 , wherein a content of the radical-polymerizable compound (C) in the radical-polymerizable resin composition is 80 to 99.9% by mass.

20. The radical-polymerizable coating composition of claim 18 , wherein the radical-polymerizable coating composition is a two-component curable coating composition comprising a main component and a curing agent, wherein the main component comprises a metal soap (A1), one or more thiol compounds (B) selected from a secondary thiol compound (B1) and a tertiary thiol compound (B2), and a radical-polymerizable compound (C), and the curing agent comprises a radical polymerization initiator (D).

21. A curable material for preventing concrete spalling, comprising the radical-polymerizable resin composition of claim 1 .

22. The radical-polymerizable resin composition of claim 1 , wherein the radical-polymerizable resin composition comprises a fiber (G).

23. A prepreg sheet produced by prepolymerizing the radical-polymerizable resin composition of claim 22 .

24. A reinforcing fiber-containing composite material comprising the radical-polymerizable resin composition of claim 22 .

25. A method for producing the radical-polymerizable resin composition of claim 1 , wherein the method comprises a step 1 of mixing the metal-containing compound (A) and the radical-polymerizable compound (C) to prepare a liquid mixture (i), and a step 2 of mixing the liquid mixture (i) and the thiol compound (B) to prepare a liquid mixture (ii).

26. The method for producing a radical-polymerizable resin composition of claim 25 , wherein the method comprises a step 3 of mixing the liquid mixture (ii) and the radical polymerization initiator (D).

27. A method for repairing a concrete structure, which comprises applying one or more repairing materials for inorganic structure of claim 13 directly or indirectly onto a surface of a damaged part of a concrete structure and curing the applied material for repairing the damaged part.

28. A photocuring method for a radical-polymerizable resin composition, wherein the method comprises a step of irradiating the radical-polymerizable resin composition of claim 8 with a light within a photosensitive wavelength range of the photoradical polymerization initiator to polymerize the radical-polymerizable compound (C).

29. A method for producing a prepreg sheet, wherein the method comprises a step of irradiating the radical-polymerizable resin composition of claim 8 with a light within a photosensitive wavelength range of the photoradical polymerization initiator to prepolymerize the radical-polymerizable compound (C).

3

Assignees

• Showa Denko Kk

Inventors

• Kuroki Kunihiro
• Miura Kenji
• Sakaguchi Yoichiro
• Saito Kohei

Classifications

• C09D201/02

  characterised by the presence of specified groups {, e.g. terminal or pendant functional groups} · CPC title

• C08K5/0091

  Complexes with metal-heteroatom-bonds · CPC title

• C08F283/01

  on to unsaturated polyesters {(C08F283/004 takes precedence)} · CPC title

• C08F299/00

  Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers · CPC title

• C09D5/00

  Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced {(electrically insulating plastics, resins or waxes H01B3/30)}; Filling pastes · CPC title