Water/oil resistant composition, article treated therewith, and processes for their production

Abstract

To provide a water/oil resistant composition which can impart a sufficient water/oil resistance to a base material even though a fluorinated copolymer having an R f group with at most 6 carbon atoms is used, said water/oil resistance being not substantially influenced by an adjuvant or the pH of dilution water, and which has little odor; an article treated therewith; and processes for their production. A water/oil resistant composition having a fluorinated copolymer dispersed or dissolved in a medium, wherein the fluorinated copolymer is one having one, some or all of amino groups in a fluorinated copolymer comprising structural units based on a monomer (a) having a C 1-6 R f group and structural units based on a monomer (b) having an amino group, converted to form a salt with an organic acid comprising an organic acid having a pKa of from 2.0 to 4.0.

1 . A water/oil resistant composition having a fluorinated copolymer dispersed or dissolved in a medium, wherein the fluorinated copolymer is one having some or all of —N(R 5 )(R 6 ) in a fluorinated copolymer comprising from 50 to 98 mass % of structural units based on the following monomer (a) and from 2 to 50 mass % of structural units based on the following monomer (b), converted to form a salt with an organic acid comprising an organic acid having a pKa of from 2.0 to 4.0,
 Monomer (a): a compound represented by the following formula (1):
   (Z—Y) n X   (1)
 
 
 wherein Z is a C 1-6  polyfluoroalkyl group or a group represented by the following formula (2), Y is a bivalent organic group or a single bond, n is 1 or 2, and X is any one of groups represented by the following formulae (3-1) to (3-5) when n is 1, or any one of groups represented by the following formulae (4-1) to (4-4) when n is 2,
   C m F 2m+1 O(CF 2 CF(CF 3 )O) d CF(CF 3 )—  (2)
 
 
 wherein m is an integer of from 1 to 6, and d is an integer of from 1 to 4,
   —C(R)═CH 2    (3-1)
 
   —C(O)OC(R)═CH 2    (3-2)
 
   —OC(O)C(R)═CH 2    (3-3)
 
   —OCH 2 -φ-C(R)═CH 2    (3-4)
 
   —OCH═CH 2    (3-5)
 
 
 wherein R is a hydrogen atom, a methyl group or a halogen atom, and φ is a phenylene group,
   —CH[—CH 2 ) p C(R)═CH 2 ]—  (4-1)
 
   —CH[—CH 2 ) p C(O)OC(R)═CH 2 ]—  (4-2)
 
   —CH[—CH 2 ) p OC(O)C(R)═CH 2 ]—  (4-3)
 
   —OC(O)CH═CHC(O)O—  (4-4)
 
 
 wherein R is a hydrogen atom, a methyl group or a halogen atom, and p is an integer of from 0 to 4, 
 Monomer (b): a compound represented by the following formula (5):
   CH 2 ═C(R 4 )C(O)O-Q-N(R 5 )(R 6 )   (5)
 
 
 wherein R 4  is a hydrogen atom or a methyl group, Q is a group having one, some or all of hydrogen atoms in a C 2-3  alkylene group, substituted by hydroxy groups, or a C 2-4  alkylene group, and each of R 5  and R 6  which are independent of each other, is a benzyl group or a C 1-8  alkyl group, or R 5  and R 6  are bonded to form a morpholino group, a piperidino group or a pyrrolidinyl group together with the nitrogen atom. 
 
     
     
         2 . The water/oil resistant composition according to  claim 1 , wherein the organic acid having a pKa of from 2.0 to 4.0 is at least one member selected from the group consisting of lactic acid, citric acid, malic acid and itaconic acid. 
     
     
         3 . The water/oil resistant composition according to  claim 1 , which further contains an adjuvant. 
     
     
         4 . The water/oil resistant composition according to  claim 3 , which contains, as the adjuvant, at least one member selected from the group consisting of an anionic paper strength enhancing agent, an anionic defoaming agent, an anionic sizing agent and an anionic chelating agent. 
     
     
         5 . The water/oil resistant composition according to  claim 1 , wherein the fluorinated copolymer further contains structural units based on the following monomer (c):
 Monomer (c): a compound represented by the following formula (6):
   CH 2 ═C(R f )-G-(R 2 O) q -R 3    (6)
 
   wherein R 1  is a hydrogen atom or a methyl group, G is a group represented by the following formula (7-1) or (7-2), R 2  is a C 2-4  alkylene group and two or more alkylene groups different in the number of carbon atoms may be contained in one molecule, q is an integer of from 1 to 50, and R 3  is a hydrogen atom or a methyl group,
   —C(O)O—(CH 2 ) r —  (7-1)
 
   —C(O)O—(CH 2 ) r —NHC(O)O—  (7-2)
 
   wherein r is an integer of from 0 to 4.   
     
     
         6 . The water/oil resistant composition according to  claim 1 , wherein the fluorinated copolymer further contains structural units based on the following monomer (d):
 Monomer (d): a compound having a blocked isocyanate group, an alkoxysilyl group, a glycidyl group or an oxyalkylene group, and a polymerizable unsaturated group, and not having a polyfluoroalkyl group, and when it has a polyoxyalkylene group, it has polymerizable unsaturated groups at both terminals (provided that monomers (a) to (c) are excluded).   
     
     
         7 . Water/oil resistant paper having a base material treated with the water/oil resistant composition as defined in  claim 1 . 
     
     
         8 . A process for producing a water/oil resistant composition, which comprises:
 a step of polymerizing a monomer mixture comprising from 50 to 98 mass % of the following monomer (a) and from 2 to 50 mass % of the following monomer (b) to obtain a fluorinated copolymer, and   a step of converting some or all of —N(R 5 )(R 6 ) in the fluorinated copolymer to form a salt with an organic acid comprising an organic acid having a pKa of from 2.0 to 4.0 and dispersing or dissolving the fluorinated copolymer in a medium,   Monomer (a): a compound represented by the following formula (1):
   (Z—Y) n X   (1)
 
   wherein Z is a C 1-6  polyfluoroalkyl group or a group represented by the following formula (2), Y is a bivalent organic group or a single bond, n is 1 or 2, and X is any one of groups represented by the following formulae (3-1) to (3-5) when n is 1, or any one of groups represented by the following formulae (4-1) to (4-4) when n is 2,
   C m F 2m+1 (CF 2 CF(CF 3 )O) d CF(CF 3 )—  (2)
 
   wherein m is an integer of from 1 to 6, and d is an integer of from 1 to 4,
   —C(R)═CH 2    (3-1)
 
   C(O)OC(R)═CH 2    (3-2)
 
   —OC(O)C(R)═CH 2    (3-3)
 
   —OCH 2 -φ-C(R)═CH 2    (3-4)
 
   —OCH═CH 2    (3-5)
 
   wherein R is a hydrogen atom, a methyl group or a halogen atom, and φ is a phenylene group,
   —CH[—CH 2 ) p C(R)═CH 2 ]—  (4-1)
 
   —CH[(CH 2 ) p C(O)OC(R)═CH 2 ]—  (4-2)
 
   —CH[(CH 2 ) p OC(O)C(R)═CH 2 ]—  (4-3)
 
   —OC(O)CH═CHC(O)O—tm (4-4)
 
   wherein R is a hydrogen atom, a methyl group or a halogen atom, and p is an integer of from 0 to 4,   Monomer (b): a compound represented by the following formula (5):
   CH 2 ═C(R 4 )C(O)O-Q-N(R 5 )(R 6 )   (5)
 
   wherein R 4  is a hydrogen atom or a methyl group, Q is a group having one, some or all of hydrogen atoms in a C 2-3  alkylene group, substituted by hydroxy groups, or a C 2-4  alkylene group, and each of R 5  and R 6  which are independent of each other, is a benzyl group or a C 1-8  alkyl group, or R 5  and R 6  are bonded to form a morpholino group, a piperidino group or a pyrrolidinyl group together with the nitrogen atom.   
     
     
         9 . The process for producing a water/oil resistant composition according to  claim 8 , wherein the organic acid is from 5 to 80 parts by mass per 100 parts by mass of the fluorinated copolymer. 
     
     
         10 . The process for producing a water/oil resistant composition according to  claim 8 , wherein the organic acid having a pKa of from 2.0 to 4.0 is at least one member selected from the group consisting of lactic acid, citric acid, malic acid and itaconic acid. 
     
     
         11 . The process for producing a water/oil resistant composition according to  claim 8 , which further contains a step of adding an adjuvant. 
     
     
         12 . The process for producing a water/oil resistant composition according to  claim 11 , wherein the adjuvant is at least one member selected from the group consisting of an anionic paper strength enhancing agent, an anionic defoaming agent, an anionic sizing agent and an anionic chelating agent. 
     
     
         13 . The process for producing a water/oil resistant composition according to  claim 8 , wherein the monomer mixture further contains the following monomer (c):
 Monomer (c): a compound represented by the following formula (6):
   CH 2 ═C(R 1 )-G-(R 2 O) q —R 3    (6)
 
   wherein R 1  is a hydrogen atom or a methyl group, G is a group represented by the following formula (7-1) or (7-2), R 2  is a C 2-4  alkylene group and two or more alkylene groups different in the number of carbon atoms may be contained in one molecule, q is an integer of from 1 to 50, and R 3  is a hydrogen atom or a methyl group,
   —C(O)O(CH 2 ) r —  (7-1)
 
   C(O)O—(CH 2 ) r —NHC(O)O—  (7-2)
 
   wherein r is an integer of from 0 to 4.   
     
     
         14 . The process for producing a water/oil resistant composition according to  claim 8 , wherein the monomer mixture further contains the following monomer (d):
 Monomer (d): a compound having a blocked isocyanate group, an alkoxysilyl group, a glycidyl group or an oxyalkylene group, and a polymerizable unsaturated group, and not having a polyfluoroalkyl group, and when it has a polyoxyalkylene group, it has polymerizable unsaturated groups at both terminals (provided that monomers (a) to (c) are excluded).   
     
     
         15 . A process for producing water/oil resistant paper, which comprises treating a base material with the water/oil resistant composition obtained by the process as defined in  claim 8 .