Curing accelerator for oxidatively polymerized unsaturated resin, printing ink, and paint

Patent metadata

Field	Value
Publication number	US-11053372-B2
Application number	US-201816614915-A
Country	US
Kind code	B2
Filing date	May 15, 2018
Priority date	Jun 8, 2017
Publication date	Jul 6, 2021
Grant date	Jul 6, 2021

Abstract

Provided are a curing accelerator for an oxidative polymerization type unsaturated resin having a high curing accelerating ability, and a printing ink and a coating material. Specifically, there are provided a curing accelerator for an oxidative polymerization type unsaturated resin, containing a metal complex (β) having an anion compound (α) represented by the following structural formula (1-1) or (1-2) as a ligand:wherein R1 is any one of a hydroxyl group, an amino group, a nitro group, a nitroso group, a sulfo group, a halogen atom, a hydrocarbon group which may have a substituent, a hydrocarbon oxy group which may have a substituent, and a hydrocarbon oxycarbonyl group which may have a substituent, m is 0 or an integer of 1 to 3, n is 0 or an integer of 1 to 6, and X is any one of a carboxylate group, a hydrogen atom, and the R1 group.

First claim

The invention claimed is:

1. A curing accelerator for an oxidative polymerization type unsaturated resin, comprising:
a metal complex (β) having manganese or iron as a central metal and having an anion compound (a) represented by the following structural formula (1-1) or (1-2) as a ligand:

wherein R 1 is any one of a hydroxyl group, an amino group, a nitro group, a nitroso group, a sulfo group, a halogen atom, a hydrocarbon group which may have a substituent, a hydrocarbon oxy group which may have a substituent, and a hydrocarbon oxycarbonyl group which may have a substituent, m is 0 or an integer of 1 to 3, n is 0 or an integer of 1 to 6, and X is any one of a carboxylate group, a hydrogen atom, and a R 1 group;
at least one of an imidazole compound (C); and
a benzyl alcohol compound (D).

2. A curable resin composition comprising an oxidative polymerization type unsaturated resin and a curing accelerator for an oxidative polymerization type unsaturated resin, comprising a metal complex (β) having manganese or iron as a central metal and having an anion compound (α) represented by the following structural formula (1-1) or (1-2) as a ligand:

wherein R 1 is any one of a hydroxyl group, an amino group, a nitro group, a nitroso group, a sulfo group, a halogen atom, a hydrocarbon group which may have a substituent, a hydrocarbon oxy group which may have a substituent, and a hydrocarbon oxycarbonyl group which may have a substituent, m is 0 or an integer of 1 to 3, n is 0 or an integer of 1 to 6, and X is any one of a carboxylate group, a hydrogen atom, and a R 1 group.

3. The curable resin composition according to claim 2 , which is a printing ink or a coating material.

4. A method for preparing a curable resin composition of claim 2 , comprising mixing a compound (A) represented by the following structural formula (2-1) or (2-2):

wherein R 1 is any one of a hydroxyl group, an amino group, a nitro group, a nitroso group, a sulfo group, a halogen atom, a hydrocarbon group which may have a substituent, a hydrocarbon oxy group which may have a substituent, and a hydrocarbon oxycarbonyl group which may have a substituent, m is 0 or an integer of 1 to 3, n is 0 or an integer of 1 to 6, and X is any one of a carboxy group, a hydrogen atom, and a R 1 group; a metal salt (B) of manganese or iron; and an oxidative polymerization type unsaturated resin.

5. A curing accelerator for an oxidative polymerization type unsaturated resin, comprising:
a metal complex (β2) having an anion compound (α) represented by the following structural formula (1-1) or (1-2) as a ligand:

wherein R 1 is any one of a hydroxyl group, an amino group, a nitro group, a nitroso group, a sulfo group, a halogen atom, a hydrocarbon group which may have a substituent, a hydrocarbon oxy group which may have a substituent, and a hydrocarbon oxycarbonyl group which may have a substituent, m is 0 or an integer of 1 to 3, n is 0 or an integer of 1 to 6, and X is any one of a carboxylate group, a hydrogen atom, and a R 1 group, wherein
the metal complex (β2) comprises a metal salt represented by the following general formula (B-1):
M(X) n   (B-1)

wherein M is manganese or iron as a central metal, X is any one of F − , Cl − , Br − , I − , PF 6 − , SbF 6 − , AsF 6 − , BF 4 − , B(C 6 F 5 ) 4 − , ClO 4 − , ClO 3 − , CO 2 − , ClO − , H 2 PO 4 − , H 2 PO 3 − , H 2 PO 2 − , HCO 3 − , NO 3 − , NO 2 − , (CH 3 CO) 2 CH − , RCOO − (wherein R is a hydrocarbon group having 1 to 22 carbon atoms), O 2- , S 2- , SO 4 2- , SO 3 2- , and CO 3 2- ; and n is an integer of 1 or more;
at least one of an imidazole compound (C); and
a benzyl alcohol compound (D).

6. A curable resin composition comprising an oxidative polymerization type unsaturated resin and a curing accelerator for an oxidative polymerization type unsaturated resin, comprising a metal complex (β2) having an anion compound (α) represented by the following structural formula (1-1) or (1-2) as a ligand:

wherein R 1 is any one of a hydroxyl group, an amino group, a nitro group, a nitroso group, a sulfo group, a halogen atom, a hydrocarbon group which may have a substituent, a hydrocarbon oxy group which may have a substituent, and a hydrocarbon oxycarbonyl group which may have a substituent, m is 0 or an integer of 1 to 3, n is 0 or an integer of 1 to 6, and X is any one of a carboxylate group, a hydrogen atom, and a R 1 group, wherein
the metal complex (β2) comprises a metal salt represented by the following general formula (B-1):
M(X) n   (B-1)

wherein M is manganese or iron as a central metal, X is any one of F − , Cl − , Br − , I − , PF 6 − , SbF 6 − , AsF 6 − , BF 4 − , B(C 6 F 5 ) 4 − , ClO 4 − , ClO 3 − , CO 2 − , ClO − , H 2 PO 4 − , H 2 PO 3 − , H 2 PO 2 − , HCO 3 − , NO 3 − , NO 2 − , (CH 3 CO) 2 CH − , RCOO − (wherein R is a hydrocarbon group having 1 to 22 carbon atoms), O 2- , S 2- , SO 4 2- , SO 3 2- , and CO 3 2- ; and n is an integer of 1 or more.

7. The curable resin composition according to claim 6 , which is a printing ink or a coating material.

8. A method for preparing a curable resin composition of claim 6 , comprising mixing a compound (A) represented by the following structural formula (2-1) or (2-2):

wherein R 1 is any one of a hydroxyl group, an amino group, a nitro group, a nitroso group, a sulfo group, a halogen atom, a hydrocarbon group which may have a substituent, a hydrocarbon oxy group which may have a substituent, and a hydrocarbon oxycarbonyl group which may have a substituent, m is 0 or an integer of 1 to 3, n is 0 or an integer of 1 to 6, and X is any one of a carboxy group, a hydrogen atom, and a R 1 group; a metal salt (B) of manganese or iron; and an oxidative polymerization type unsaturated resin.

9. A curable resin composition comprising:
a curing accelerator for an oxidative polymerization type unsaturated resin, comprising a compound (A) represented by the following structural formula (2-1) or (2-2):

wherein R 1 is any one of a hydroxyl group, an amino group, a nitro group, a nitroso group, a sulfo group, a halogen atom, a hydrocarbon group which may have a substituent, a hydrocarbon oxy group which may have a substituent, and a hydrocarbon oxycarbonyl group which may have a substituent, m is 0 or an integer of 1 to 3, n is 0 or an integer of 1 to 6, R 2 is a hydrogen atom or an aliphatic hydrocarbon group, and X is any one of —COOR 2 group, a hydrogen atom, and a R 1 group, and a metal salt (B) comprising a manganese salt or an iron salt as an essential component; and
at least one oxidative polymerization type unsaturated resin selected from a rosin-modified phenolic resin, an alkyd resin, a petroleum resin, polymerized oil, an unsaturated group-containing urethane resin, and an unsaturated group-containing epoxy resin.

10. The curable resin composition accord

Assignees

• Dainippon Ink & Chemicals

Inventors

• Takahashi Akinori
• ODASHIMA Takayuki

Classifications

• C09D11/105

  Alkyd resins · CPC title

• C09D161/14

  Modified phenol-aldehyde condensates · CPC title

• C09D11/03

  characterised by features other than the chemical nature of the binder · CPC title

• C07D215/14

  Radicals substituted by oxygen atoms · CPC title

• C08G8/34

  by natural resins or resin acids, e.g. rosin · CPC title