Surfactant mixtures

Patent metadata

Field	Value
Publication number	US-10590262-B2
Application number	US-201314418970-A
Country	US
Kind code	B2
Filing date	Jul 26, 2013
Priority date	Aug 6, 2012
Publication date	Mar 17, 2020
Grant date	Mar 17, 2020

Abstract

The present invention relates to novel surfactant mixtures comprising at least one compound A whose dynamic surface tension γ dyn. at a use concentration of 0.1% by weight and a bubble lifetime of 100 ms is <45 mN/m, and at least one compound B whose static surface tension y stat measured at a use concentration of 0.1% by weight is less than or equal to the static surface tension Y stat of compound A, to the use thereof as additives, for example in preparations for surface coating, such as paints, lacquers, protective coatings and special coatings in electronic or in optical applications. At least one compound in the novel surfactant mixture is a fluorosurfactant.

First claim

The invention claimed is:

1. A surfactant mixture comprising at least one compound A whose dynamic surface tension γ dyn. measured according to the bubble pressure method at 20° C.±0.2° C. at a use concentration of 0.1% by weight and a bubble lifetime of 100 ms is ≤35 mN/m, and at least one compound B whose static surface tension γ stat. is ≤the static surface tension γ stat. of compound A, wherein at least one of the compounds A and at least one of the compounds B is a fluorosurfactant
wherein the static surface tension γ stat. is measured by the Wilhelmy plate method at 20° C.±0.2° C. at a use concentration of 0.1% by weight,
wherein the static surface tension γ stat. of the surfactant mixture is lower than the static surface tensions γ stat. of the individual surfactants,
wherein the compound B has static surface tension γ stat. of ≤20 mN/m,
wherein said mixture comprises the compounds A and B in a weight ratio A/B of 10:90 to 90:10,
wherein said mixture comprises as compound A and/or compound B at least one compound of the formula (I)

where
X is a hydrophilic group,
R is linear or branched alkylene, where one or more non-adjacent C atoms may be replaced by O, S and/or N,
r is 0 or 1,
B is a single bond, O, NH, NR′, CH 2 , C(O)—O, S, CH 2 —O, O—C(O), O—C(O)—O, SiR′ 2 —O, O—SO 2 or SO 2 —O, where R′ is linear or branched alkyl,
R 1 and R 2 are, independently of one another, hydrogen or —CH 2 —COY 3 -L 3 -(A 3 ) n3 ,
Y 1 , Y 2 and Y 3 are, independently of one another, O, S or N,
L 1 , L 2 and L 3 are, independently of one another, linear or branched alkylene,
where one or more non-adjacent C atoms may be replaced by O, S and/or N,
A 1 , A 2 and A 3 are, independently of one another, hydrogen or a group of the structure —Z i (CR 3 R 4 ) mi Rf i , where i is 1, 2 or 3,
Z i is 0, S or N and is bonded to a C atom of L i or is a single bond,
R 3 and R 4 are, independently of one another, hydrogen or an alkyl group,
Rf i is a fluorine-containing radical,
n1, n2 and n3 are, independently of one another, 1-6,
m1, m2 and m3 are, independently of one another, 0-5,
and the compounds of formula (I) contain at least one Rf i group
and
wherein said mixture comprises at least one compound of the formula (II)
(RF-(spacer) m ) n M  (II)

where
the RF-(spacer) m group is equal to C n′ F 2n′+1 —, C n′ F 2n′+1 —CH 2 CH 2 —, C n′ F 2n′+1 —OCF 2 CF 2 —, C n′ F 2n′+1 —OC 6 H 4 —, C n′ F 2n′+1 —C(O)NH(CH 2 ) 3 N═, C n′ F 2n′+1 —SO 2 NH(CH 2 ) 3 N═, CF 3 CCl 2 (CF 2 CFCl) n′+1 —CF 2 — or C 8 F 17 CH 2 CH 2 Si(CH 3 ) 2 —, where n′=4-12, and
M is equal to —OPOO − , —COO − , —SO 3 − , —OSO 3 − , —OP(O)(O − )O— or —OP(O)O 2 2−
n is ≥1,
and
wherein said at least one compound of the Formula (II) is at least one compound A or at least one compound B.

2. The surfactant mixture according to claim 1 , wherein the compounds A have a dynamic surface tension γ dyn. of ≤30 mN/m and the compounds B have a static surface tension γ stat. of ≤20 mN/m.

3. The surfactant mixture according to claim 1 , wherein said compound of the formula (I) is a compound of the formulae (III), (IV) and/or (V):

where
X is equal to —SO 3 − , —OSO 3 − , —PO 3 2− or OPO 3 2− ,
Y 1 , Y 2 , Y 3 , Z 1 , Z 2 and Z 3 are equal to O,
Rf 1 , Rf 2 and Rf 3 are equal to perfluorinated groups Rf i having 1 to 4 C atoms,
n1, n2 and n3 are equal to 1 or 2,
m1, m2 and m3 are equal to 1-4,
L 1 , L 2 and L 3 are equal to linear or branched C3-C6-alkylene,
R 3 and R 4 are equal to hydrogen or an alkyl group having 1 to 3 C atoms.

4. The surfactant mixture according to claim 1 , wherein in the compound of the formula (II), where M is equal to —OPOO − , —COO − , —SO 3 − , —OSO 3 − , —OP(O)(O − )O— or —OP(O)O 2 2−
with H + , Na + , K + , Li + or NH 4 + as counterion.

5. The surfactant mixture according to claim 1 , wherein said mixture comprises a compound of the formula (IV)

where
X is equal to —SO 3 − , —OSO 3 − , —PO 3 2− or OPO 3 2− ,
Y 1 , Y 2 , Y 3 , Z 1 , Z 2 and Z 3 are equal to O,
Rf 1 , Rf 2 and Rf 3 are equal to perfluorinated groups Rf i having 1 to 4 C atoms,
n1, n2 and n3 are equal to 1 or 2,
m1, m2 and m3 are equal to 1-4,
L 1 , L 2 and L 3 are equal to linear or branched C3-C6-alkylene,
R 3 and R 4 are equal to hydrogen or an alkyl group having 1 to 3 C atoms and a compound of the formula (II)
(RF-(spacer) m ) n M  (II)

where (RF-(spacer) m ) n - is equal to C n′ F 2n′+1 —CH 2 CH 2 — and M is equal to —OPOO − , and n′=4-12 and with Na + as counterion wherein said at least one compound of the Formula (IV) is at least one compound A or at least one compound B
and
wherein said at least one compound of the Formula (II) is at least one compound A or at least one compound B.

6. The surfactant mixture according to claim 1 , wherein said mixture further comprises at least one compound of the formulae (VII) to (X)

where x=1-500, y=1-500 and R=phenyl, methyl or —(O—C 2 H 3 R′) n″ —OR″, where n″=1-1000, R′=linear and branched alkyl radical and R″=linear and branched alkyl radicals,
M 2 (D′E n′″ )PM  (IX)

where M=(CH 3 ) 3 SiO—, D′=Si(CH 3 )(R′″), E=OCH 2 CH 2 , n′″=5-40 and P=OH, OMe or OAc, where R′″=linear and/or branched alkyl chain,

where n=1-100.

7. A composition comprising the surfactant mixture according to claim 1 and a vehicle.

8. The composition according to claim 7 , wherein said composition is a paint, a coating preparation, a fire-extinguishing agent, a lubricant, a washing agent, a detergent, a de-icer, a hydrophobicisation agent for textile finishing or glass treatment, a floor polish, an adhesive, a developer solution, a rinse solution, an immersion oil or a photoresists for a photolithographic process.

9. A method comprising incorporating the surfactant mixture according to claim 1 as an additive into a paint, a lacquer, a printing ink, a protective coating, a coating in an electronic or optical application, a photoresist, a top antireflective coating, a bottom antireflective coating, a photographic coating, a coating of an optical element, a floor polish, an adhesive, a fire-extinguishing agent, a lubricant, a washing agent, a detergent, a de-icer, a developer solution, a rinse solution, an immersion oil or a photoresist for a photolithographic process.

10. A compound of formula (IV-1)

wherein * defines the point of attachment.

11. A composition comprising the compound of the formulae (IV-1) of claim 10 and a vehicle.

12. The composition according to claim 11 , wherein said composition is a paint, a coating preparation, a fire-extinguishing agent, a lubricant, a washing agent, a det

Assignees

• Merck Patent Gmbh

Inventors

• Pahnke Joerg
• Jonschker Gerhard
• Schellenberger Steffen
• Kaiser Mathias

Classifications

• C08K5/0008

  Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59 · CPC title

• C08K5/11

  of acyclic polycarboxylic acids · CPC title

• C10M137/04

  Phosphate esters · CPC title

• C10M129/72

  of polycarboxylic acids · CPC title

• C08K5/51

  Phosphorus bound to oxygen · CPC title