Curable resin composition

Patent metadata

Field	Value
Publication number	US-9932447-B2
Application number	US-201414915981-A
Country	US
Kind code	B2
Filing date	Aug 22, 2014
Priority date	Sep 3, 2013
Publication date	Apr 3, 2018
Grant date	Apr 3, 2018

Abstract

Provided is a curable resin composition which exhibits excellent curability and is good in storage stability. The curable resin composition comprises (a) a polymer having a hydrolyzable silyl group, (b) an acid catalyst, and (c) an onium salt represented by the following general formula (1):

C + A −   (1)
wherein C + is an onium cation, and A − is a hydrogen sulfate anion, a hydrogen sulfite anion, a sulfonate anion represented by R 1 SO 3 − wherein R 1 represents an alkyl group, perfluoroalkyl group, cycloalkyl group, vinyl group, aryl group, perfluoroaryl group, aralkyl group or halogen atom; or a bis(substituted sulfonyl)imide anion represented by (R 2 SO 2 ) 2 N − wherein R 2 represents an alkyl group, perfluoroalkyl group, or aryl group; tetrafluoroborate anion, or hexafluorophosphate anion.

First claim

The invention claimed is:

1. A curable resin composition which comprises (a) a polymer having a hydrolyzable silyl group, (b) an acid catalyst having a pKa of 4 or lower at 25° C., and (c) an onium salt represented by the following general formula (1):
C + A −   (1)

wherein C + is an onium cation, and A − is a hydrogen sulfate anion, a hydrogen sulfite anion, a sulfonate anion represented by R 1 SO 3 − wherein R 1 represents an alkyl group, perfluoroalkyl group, cycloalkyl group, vinyl group, aryl group, perfluoroaryl group, aralkyl group or halogen atom; or a bis(substituted sulfonyl)imide anion represented by (R 2 SO 2 ) 2 N − wherein R 2 represents an alkyl group, perfluoroalkyl group, or aryl group; tetrafluoroborate anion, or hexafluorophosphate anion,
wherein the main chain chemical structure of the polymer (a) having a hydrolyzable silyl group is at least one polymer selected from the group consisting of oxyalkylene polymer, vinyl polymer, polyester polymer, polyurethane polymer and polycarbonate polymer,
said curable resin composition containing the acid catalyst (b) in an amount of from 0.002 to 2 parts by mass, relative to 100 parts by mass of the polymer (a) having a hydrolyzable silyl group,
said curable resin composition containing the onium salt (c) in an amount of from 0.005 to 10 parts by mass, relative to 100 parts by mass of the polymer (a) having a hydrolyzable silyl group, and
wherein the cation of the onium salt (c) is at least one onium cation selected from the group consisting of quaternary ammonium cation, imidazolium cation, and pyridinium cation.

2. The curable resin composition according to claim 1 , wherein the polymer (a) having a hydrolyzable silyl group has a number average molecular weight of from 500 to 50,000.

3. The curable resin composition according to claim 1 , wherein the anion of the onium salt (c) is at least one anion selected from the group consisting of hydrogen sulfate anion, perfluoroalkylsulfonate anion, and bis(perfluoroalkane sulfonyl)imide anion.

4. A curable resin composition which comprises (a) a polymer having a hydrolyzable silyl group, (b) an acid catalyst having a pKa of 4 or lower at 25° C., and (c) an onium salt represented by the following general formula (1):
C + A −   (1)

wherein C + is an onium cation, and A − is a hydrogen sulfate anion, a hydrogen sulfite anion, a sulfonate anion represented by R 1 SO 3 − wherein R 1 represents an alkyl group, perfluoroalkyl group, cycloalkyl group, vinyl group, aryl group, perfluoroaryl group, aralkyl group or halogen atom; or a bis(substituted sulfonyl)imide anion represented by (R 2 SO 2 ) 2 N − wherein R 2 represents an alkyl group, perfluoroalkyl group, or aryl group; tetrafluoroborate anion, or hexafluorophosphate anion,
wherein the main chain chemical structure of the polymer (a) having a hydrolysable silyl group is at least one polymer selected from the group consisting of oxyalkylene polymer, vinyl polymer, polyester polymer, polyurethane polymer and polycarbonate polymer,
said curable resin composition containing the acid catalyst (b) in an amount of from 0.002 to 2 parts by mass, relative to 100 parts by mass of the polymer (a) having a hydrolyzable silyl group,
said curable resin composition containing the onium salt (c) in an amount of from 0.005 to 10 parts by mass, relative to 100 parts by mass of the polymer (a) having a hydrolyzable silyl group, and
wherein the onium cation of the onium salt (c) comprises a quaternary ammonium cation.

5. A curable resin composition which comprises (a) a polymer having a hydrolyzable silyl group, (b) an acid catalyst having a pKa of 4 or lower at 25° C., and (c) an onium salt represented by the following general formula (1):
C + A −   (1)

wherein C + is an onium cation, and A − is a hydrogen sulfate anion, a hydrogen sulfite anion, a sulfonate anion represented by R 1 SO 3 − wherein R 1 represents an alkyl group, perfluoroalkyl group, cycloalkyl group, vinyl group, aryl group, perfluoroaryl group, aralkyl group or halogen atom; or a bis(substituted sulfonyl)imide anion represented by (R 2 SO 2 ) 2 N − wherein R 2 represents an alkyl group, perfluoroalkyl group, or aryl group; tetrafluoroborate anion, or hexafluorophosphate anion,
wherein the main chain chemical structure of the polymer (a) having a hydrolysable silyl group is at least one polymer selected from the group consisting of oxyalkylene polymer, vinyl polymer, polyester polymer, polyurethane polymer and polycarbonate polymer,
said curable resin composition containing the acid catalyst (b) in an amount of from 0.002 to 2 parts by mass, relative to 100 parts by mass of the polymer (a) having a hydrolyzable silyl group,
said curable resin composition containing the onium salt (c) in an amount of from 0.005 to 10 parts by mass, relative to 100 parts by mass of the polymer (a) having a hydrolyzable silyl group, and
wherein the onium cation of the onium salt (c) comprises an imidazolium cation.

6. A curable resin composition which comprises (a) a polymer having a hydrolyzable silyl group, (b) an acid catalyst having a pKa of 4 or lower at 25° C., and (c) an onium salt represented by the following general formula (1):
C + A −   (1)

wherein C + is an onium cation, and A − is a hydrogen sulfate anion, a hydrogen sulfite anion, a sulfonate anion represented by R 1 SO 3 − wherein R 1 represents an alkyl group, perfluoroalkyl group, cycloalkyl group, vinyl group, aryl group, perfluoroaryl group, aralkyl group or halogen atom; or a bis(substituted sulfonyl)imide anion represented by (R 2 SO 2 ) 2 N − wherein R 2 represents an alkyl group, perfluoroalkyl group, or aryl group; tetrafluoroborate anion, or hexafluorophosphate anion,
wherein the main chain chemical structure of the polymer (a) having a hydrolysable silyl group is at least one polymer selected from the group consisting of oxyalkylene polymer, vinyl polymer, polyester polymer, polyurethane polymer and polycarbonate polymer,
said curable resin composition containing the acid catalyst (b) in an amount of from 0.002 to 2 parts by mass, relative to 100 parts by mass of the polymer (a) having a hydrolyzable silyl group,
said curable resin composition containing the onium salt (c) in an amount of from 0.005 to 10 parts by mass, relative to 100 parts by mass of the polymer (a) having a hydrolyzable silyl group, and
wherein the onium cation of the onium salt (c) comprises a pyridinium cation.

7. The curable resin composition according to claim 2 , wherein the acid catalyst (b) is at least one acid selected from the group consisting of sulfonic acid, hydrochloric acid, nitric acid, phosphoric acid, phosphoric acid monoester, phosphoric acid diester, phosphorous acid, phosphorous acid ester, hypophosphorous acid, halogenated alkylcarboxylic acid, and halogenated arylcarboxylic acid.

8. A cured product obtained by curing a curable composition according to claim 1 .

Assignees

• Toagosei Co Ltd

Inventors

• Ishizaki Kenichi
• Ando Yushi

Classifications

• C08L101/10 Primary

  containing hydrolysable silane groups · CPC title

• C08K5/42

  Sulfonic acids; Derivatives thereof · CPC title

• C08K5/43

  Compounds containing sulfur bound to nitrogen · CPC title

• C08K5/3432

  Six-membered rings · CPC title

• C08G77/38 Primary

  Polysiloxanes modified by chemical after-treatment · CPC title