Amphoteric polymer resins that increase the rate of sizing development

Abstract

Amphoteric promoter resin that is a polymerization reaction product of a quaternary diallylammonium monomer, a diallylammonium monomer, and a unsaturated organic acid as well as compositions containing the amphoteric promoter resin and a sizing agent. The method of sizing paper with such amphoteric promoter resin compound and a sizing agent provides sized paper with significantly improved sizing property characteristics, and the sized paper exhibits superior retention of brightness due to added optical brighteners.

What is claimed is:  
     
         1 . A water soluble amphoteric promoter resin composition for promoting sizing of paper that is a polymerization reaction product of monomer comprising at least one quaternary diallyl ammonium monomer of formula (III):  
       
         
           
           
               
               
           
         
       
       optionally, including at least 1 diallylammonium monomer of formula (IV)  
       
         
           
           
               
               
           
         
         where R 1A , R 1B , R 1C  and R 1D  are hydrogen or C 1 -C 22  straight chain or branched alkyl;  
         R 2  and R 3  are alkyl, alkenyl, aryl, heteroatom interrupted alkyl or alkenyl, wherein the heteroatoms are selected from the group N, S, and O;  
         R 4  is hydrogen, alkyl, alkenyl aryl; heteroatom interrupted alkyl or alkenyl, wherein the heteroatoms are selected from the group N, S, and O; and  
         X − . is a sizing compatible anion  
         and at least one unsaturated organic acid of formula (II)  
         
           
             
             
                 
                 
             
           
         
         where R x , R y , and R z , are hydrogen, alkyl, alkenyl, aryl heteroatom interrupted alkyl or alkenyl, wherein the heteroatoms are selected from the group N, S, and O; and E is an organic substituent selected from the group COO, SO3, HSO4, and H2PO4 and  
         wherein the sum of the mole percent of the quaternary diallyl ammonium monomers of formula III and the mole percent of the diallyl ammonium monomers of formula IV constitutes at least 25% of monomers in the amphoteric promoter resin and mole percent of the unsaturated organic acid of formula II constitutes at least 25% of monomers in the amphoteric promoter resin.  
       
     
     
         2 . The composition of  claim 1  wherein the E in the monomer of formula (II) is COO.  
     
     
         3 . The composition of  claim 1  wherein, in the monomer of formula (IV), R 1C  and R 1D  are hydrogen or methyl, and R 4  is selected from the group consisting of hydrogen, methyl, benzyl, phenyl, C 2 -C 18  alkyl, octadec-dienyl, hexadec-dienyl, octadecenyl, hexadecenyl and undecenyl.  
     
     
         4 . The composition of  claim 1  wherein, in the monomers of formula (III) and formula (IV), R 1A , R 1B , R 1C , R 1D  and R 4  are hydrogen and R 2  and R 3  are methyl.  
     
     
         5 . The composition of  claim 1  wherein, in the monomers of formula (III) and formula (IV), X −  is a halide, nitrate, acetate, benzoate, sulfate or phosphate.  
     
     
         6 . The composition of  claim 1  wherein, in the monomers of formula (III) and formula (IV), X −  is chloride.  
     
     
         7 . The composition of  claim 1  wherein in the monomers of formula (II) are selected from cinnamic acid, crotonic acid, sorbic acid, acrylic acid, methacrylic acid, itaconic acid, propiolic acid, maleic acid, fumaric acid, and the half esters and anhydrides of these acids.  
     
     
         8 . The composition of  claim 1  wherein the monomers of formula (II) are acrylic or methacrylic acids.  
     
     
         9 . The composition of  claim 1  wherein the sum of the mole percent of the quaternary diallyl ammonium monomers of formula III and the mole percent of the diallyl ammonium monomers of formula IV constitutes at least 30% of monomers in the amphoteric promoter resin.  
     
     
         10 . The composition of  claim 1  wherein the sum of the mole percent of the quaternary diallyl ammonium monomers of formula III and the mole percent of the diallyl ammonium monomers of formula IV constitutes at least 40% of monomers in the amphoteric promoter resin.  
     
     
         11 . The composition of  claim 1  wherein the monomers of the anionic unsaturated organic acid of formula V is at least 33 mole % of the sum of monomers of the cationic quaternary diallyl ammonium monomer of formula (III) and cationic diallylammonium monomer of formula (IV).  
     
     
         12 . The composition of  claim 1  wherein the monomers of the anionic unsaturated organic acid acid of formula II is at least 50 mole % of the sum of monomers of the cationic quaternary diallyl ammonium monomer of formula (III) and cationic diallylammonium monomer of formula (IV).  
     
     
         13 . The composition of  claim 1  wherein the monomers of the anionic unsaturated organic acid of formula (II) is at least 65 mole % of the sum of monomers of the cationic quaternary diallyl ammonium monomer of formula (III) and cationic diallylammonium monomer of formula (IV).  
     
     
         14 . The composition of  claim 1  wherein the monomers of the cationic diallylammonium monomer of formula (IV) constitutes up to 65% of sum of the monomers of the cationic quaternary diallyl ammonium monomer of formula (III) and cationic diallylammonium monomer of formula (IV).  
     
     
         15 . The composition of  claim 1  wherein the monomers of the cationic diallylammonium monomer of formula (IV) constitutes 10 to 50% of sum of the monomers of the cationic quaternary diallyl ammonium monomer of formula (III) and cationic diallylammonium monomer of formula (IV).  
     
     
         16 . The composition of  claim 1  wherein the polymerization reaction product is prepared by polymerizing the monomers of the cationic diallylammonium monomer of formula (IV), optionally including, monomers of the cationic quaternary diallyl ammonium monomer of formula (III) and monomers of the anionic unsaturated organic acid of formula (II) using a free radical polymerization initiator.  
     
     
         17 . The composition of  claim 1  wherein the polymerization reaction product has a weight average molecular weight of at least about 10,000.  
     
     
         18 . The composition of  claim 1  wherein the polymerization reaction product has a weight average molecular weight of at least about 30,000.  
     
     
         19 . A method of producing sized paper which comprises manufacturing sized paper in the presence of a sizing agent and a water soluble amphoteric resin containing cationic ammonium groups and anionic groups and wherein the mole percent of the cationic ammonium group constitutes at least 25 mole percent in the amphoteric resin and mole percent of the anionic group constitutes at least 25 mole percent of the amphoteric resin.  
     
     
         20 . A method of  claim 19  in which an optical brightener is present.  
     
     
         21 . A method of producing sized paper which comprises manufacturing sized paper in the presence of a sizing agent and a water soluble amphoteric promoter resin that is a polymerization reaction product of monomer comprising at least one polymerizable cationic monomer of formula (I)  
       
         
           
           
               
               
           
         
         where G is a selected from alkyl, alkenyl, allyl, aryl; heteroatom interrupted alkyl or alkenyl, wherein the heteroatoms are selected from the group N, S, and O; and  
         H, K, and J are hydrogen, alkyl, akenyl, allyl, styrenyl aryl, heteroatom interrupted alkyl or alkenyl, wherein the heteroatoms are selected from the group N, S, and O;  
         and X is a sizing compatible anion;  
         at least one polymerizable organic acid of formula (II)  
         
           
             
             
                 
                 
             
           
         
         where R x , R y , and R z , are hydrogen, alkyl, alkenyl, aryl heteroatom interrupted alkyl or alkenyl, wherein the heteroatoms are selected from the group N, S, and O; and E is an organic substituent selected from the group COO, SO3, HSO4, and H2PO4;  
         and wherein the mole percent of the cationic amine monomer of formula III constitutes at least 25% of monomers in the amphoteric promoter resin and mole percent of the organic acid of formula II constitutes at least 25% of monomers in the amphoteric promoter resin.  
       
     
     
         22 . The method of  claim 21  wherein the E in the monomer of formula II is COO.  
     
     
         23 . A method of  claim 21  in which an optical brightener is present.  
     
     
         24 . A method of producing sized paper which comprises manufacturing of sized paper in the presence of a sizing agent and a water soluble amphoteric promoter resin that is a polymerization reaction product of monomer comprising at least one cationic quaternary diallyl ammonium monomer of formula (III):  
       
         
           
           
               
               
           
         
       
       optionally, including at least 1 cationic diallylammonium monomer of formula (IV)  
       
         
           
           
               
               
           
         
         where R 1A , R 1B , R 1C  and R 1D  are hydrogen or C 1 -C 22  straight chain or branched alkyl;  
         R 2  and R 3  are alkyl, alkenyl, aryl, heteroatom interrupted alkyl or alkenyl, wherein the heteroatoms are selected from the group N, S, and O;  
         R 4  is hydrogen, alkyl, alkenyl, aryl, heteroatom interrupted alkyl or alkenyl, wherein the heteroatoms are selected from the group N, S, and O; and  
         X − . is a sizing compatible anion  
         and at least one organic acid of formula (II)  
         
           
             
             
                 
                 
             
           
         
         where R x , R y , and R z , are hydrogen, alkyl, alkenyl, aryl, heteroatom interrupted alkyl or alkenyl, wherein the heteroatoms are selected from the group N, S, and O; and E is an organic substituent selected from the group COO, SO3, HSO4, and H2PO4;  
         and wherein the sum of the mole percent of the quaternary diallyl ammonium monomers of formula (III) and the mole percent of the diallyl ammonium monomers of formula (IV) constitutes at least 25% of monomers in the amphoteric promoter resin and mole percent of the unsaturated organic acid of formula (II) constitutes at least 25% of monomers in the amphoteric promoter resin.  
       
     
     
         25 . The method of  claim 24  wherein the E in the monomer of formula (II) is COO.  
     
     
         26 . A method of  claim 24  wherein, in the monomer of formula (II), R 1C  and R 1D  are hydrogen or methyl, and R 4  is selected from the group consisting of hydrogen, methyl, benzyl, phenyl, C 2 -C 18  alkyl, octadec-dienyl, hexadec-dienyl, octadecenyl, hexadecenyl and undecenyl.  
     
     
         27 . A method of  claim 24  wherein, in the monomers of formula (I) and formula (II), R 1A , R 1B , R 1C , R 1D  and R 4  are hydrogen and R 2  and R 3  are methyl.  
     
     
         28 . A method of  claim 24  wherein, in the monomers of formula (I) and formula (II), X −  is a halide, nitrate, acetate, benzoate, sulfate or phosphate.  
     
     
         29 . A method of  claim 24  wherein, in the monomers of formula (I) and formula (II), X −  is chloride.  
     
     
         30 . A method of  claim 24  wherein in the monomers of formula (II) are cinnamic acid, crotonic acid, sorbic acid, acrylic acid, methacrylic acid, itaconic acid, propiolic acid, maleic acid, and, fumaric acid.  
     
     
         31 . A method of  claim 24  wherein the monomers of formula (II) are acrylic or methacrylic acids.  
     
     
         32 . A method of  claim 24  wherein the sum of the mole percent of the quaternary diallyl ammonium monomers of formula (III) and the mole percent of the diallyl ammonium monomers of formula (IV) constitutes preferably at least 30% of monomers in the amphoteric promoter resin.  
     
     
         33 . The method of  claim 24  wherein the sum of the mole percent of the quaternary diallyl ammonium monomers of formula (III) and the mole percent of the diallyl ammonium monomers of formula II constitutes preferably at least 40% of monomers in the amphoteric promoter resin.  
     
     
         34 . The method of  claim 24  wherein the monomers of the anionic unsaturated organic acid of formula V is at least 33 mole % of the sum of monomers of the cationic quaternary diallyl ammonium monomer of formula (III) and cationic diallylammonium monomer of formula (IV).  
     
     
         35 . The method of  claim 24  wherein the monomers of the anionic unsaturated organic acid of formula (II) is at least 50 mole % of the sum of monomers of the cationic quaternary diallyl ammonium monomer of formula (III) and cationic diallylammonium monomer of formula (IV).  
     
     
         36 . The method of  claim 24  wherein the monomers of the anionic unsaturated organic acid of formula (II) is at least 65 mole % of the sum of monomers of the cationic quaternary diallyl ammonium monomer of formula (III) and cationic diallylammonium monomer of formula (IV).  
     
     
         37 . The method of  claim 24  wherein the monomers of the cationic diallylammonium monomer of formula (IV) constitutes up to 65% of sum of the monomers of the cationic quaternary diallyl ammonium monomer of formula (III) and cationic diallylammonium monomer of formula (IV).  
     
     
         38 . The method of  claim 24  wherein the monomers of the cationic diallylammonium monomer of formula (IV) constitutes 10 to 50% of sum of the monomers of the cationic quaternary diallyl ammonium monomer of formula (III) and cationic diallylammonium monomer of formula (IV).  
     
     
         39 . The method of  claim 24  wherein the sizing agent and amphoteric promoter resin are added in amounts sufficient to produced a sized paper containing from about 0.005 wt % to about 1.5 wt % of the sizing agent, and from about 0.002 wt % to about 0.6 wt % of the amphoteric promoter resin, based on the weight of the dried sized paper.  
     
     
         40 . The method of  claim 24  wherein the sizing agent and amphoteric promoter resin are added in amounts sufficient to produced a sized paper containing from about 0.025 wt % to about 0.5 wt % of the sizing agent, and from about 0.007 wt % to about 0.3 wt % of the amphoteric promoter resin, based on the weight of the dried sized paper.  
     
     
         41 . The method of  claim 24  wherein the sizing agent and amphoteric promoter resin are added in amounts sufficient to produced a sized paper containing from about 0.05 wt % to about 0.25 wt % of the sizing agent, and from about 0.012 wt % to about 0.15 wt % of the amphoteric promoter resin, based on the weight of the dried sized paper.  
     
     
         42 . The method of  claim 24  wherein optical brighteners are added in amounts sufficient to produce white paper containing up to 1.5 wt % of the optical brightener based on the weight of the dried sized paper.  
     
     
         43 . A method of  claim 24  wherein the polymerization reaction product has a weight average molecular weight of at least about 10,000.  
     
     
         44 . A method of  claim 24  wherein the polymerization reaction product has a weight average molecular weight of at least about 30,000.  
     
     
         45 . The method of  claim 24  wherein the paper sizing agent is selected from the group consisting of ketene dimer, ketene multimer, acid anhydride, organic isocyanate and rosin.  
     
     
         46 . The method of  claim 45  wherein the paper sizing agent is selected from the group consisting of alkyl ketene dimer, branched alkyl ketene dimer, alkenyl ketene dimer, alkyl ketene multimer and alkenyl ketene multimer.  
     
     
         47 . The method of  claim 45  wherein the paper sizing agent is an alkenyl succinic acid anhydride sizing agent.  
     
     
         48 . The method of  claim 45  wherein the paper sizing agent is selected from the group consisting of alkyl ketene dimer, branched alkyl ketene dimer, alkenyl ketene dimer, alkyl ketene multimer, alkenyl ketene multimer, alkenyl succinic acid anhydride, stearic anhydride, alkyl isocyanate, alkyl carbamoyl chloride, alkylated melamine, rosin, styrene acrylate and styrene maleic anhydride.  
     
     
         49 . The method of  claim 24  further comprising employing the amphoteric promoter resin in combination with the paper sizing agent as an aqueous paper sizing composition containing the sizing agent and the polymerization reaction product together in an aqueous medium.  
     
     
         50 . The method of  claim 24  further comprising employing the amphoteric promoter resin polymerization reaction product and the sizing agent in a respective weight ratio of from about 0.05:1 to about 4:1.  
     
     
         51 . The method of  claim 24  further comprising employing the amphoteric promoter resin polymerization reaction product and the sizing agent in a respective weight ratio of from about 0.2:1 to about 3:1.  
     
     
         52 . The method of  claim 24  wherein the amphoteric promoter resin is applied to the surface of the paper after the paper is formed.  
     
     
         53 . A sized paper prepared with sizing agent and a amphoteric promoter resin that is a polymerization reaction product of monomers consisting essentially of at least one quaternary diallyl ammonium monomer of formula (III):  
       
         
           
           
               
               
           
         
       
       optionally, including at least 1 diallylammonium monomer of formula (IV)  
       
         
           
           
               
               
           
         
         where R 1A , R 1B , R 1C  and R 1D  are hydrogen or C 1 -C 22  straight chain or branched alkyl;  
         R 2  and R 3  are alkyl, alkenyl, aryl, heteroatom interrupted alkyl or alkenyl, wherein the heteroatoms are selected from the group N, S, and O;  
         R 4  is hydrogen, alkyl, alkenyl aryl, heteroatom interrupted alkyl or alkenyl, wherein the heteroatoms are selected from the group N, S, and O; and  
         X − . is a sizing compatible anion  
         and at least one organic acid of formula (II)  
         
           
             
             
                 
                 
             
           
         
         where R x , R y , and R z , are hydrogen, alkyl, alkenyl, aryl heteroatom interrupted alkyl or alkenyl, wherein the heteroatoms are selected from the group N, S, and O; and E is an organic substituent selected from the group COO, SO3, HSO4, and H2PO4;  
         and wherein the sum of the mole percent of the quaternary diallyl ammonium monomers of formula (III) and the mole percent of the diallyl ammonium monomers of formula (IV) constitutes at least 25% of monomers in the amphoteric promoter resin and mole percent of the unsaturated organic acid of formula (II) constitutes at least 25% of monomers in the amphoteric promoter resin.  
       
     
     
         54 . The paper sized of  claim 53  wherein the E in the monomer of formula II is COO.  
     
     
         55 . The sized paper of  claim 53  wherein, in the monomer of formula (I), R 1A  and R 1B  are hydrogen or methyl, and R 2  and R 3  are selected from the group consisting of methyl, benzyl, C 2 -C 18  alkyl, phenyl, octadec-dienyl, hexedec-dienyl, octadecenyl, hexadecenyl and undecenyl.  
     
     
         56 . The sized paper of  claim 53  wherein, in the monomer of formula (IV), R 1C  and R 1D  are hydrogen or methyl, and R 4  is selected from the group consisting of hydrogen, methyl, benzyl, phenyl, C 2 -C 18  alkyl, octadec-dienyl, hexadec-dienyl, octadecenyl, hexadecenyl and undecenyl.  
     
     
         57 . The sized paper of  claim 53  wherein, in the monomers of formula (I) and formula (IV), R 1A , R 1B , R 1C , R 1D  and R 4  are hydrogen and R 2  and R 3  are methyl.  
     
     
         58 . The sized paper of  claim 53  wherein, in the monomers of formula (I) and formula (IV), X − is a halide, nitrate, acetate, benzoate, sulfate or phosphate.  
     
     
         59 . The sized paper of  claim 53  wherein, in the monomers of formula (I) and formula (IV), X − is chloride.  
     
     
         60 . A sized paper of  claim 53  wherein the sum of the mole percent of the quaternary diallyl ammonium monomers of formula IIIand the mole percent of the diallyl ammonium monomers of formula IV constitutes preferably at least 30% of monomers in the amphoteric promoter resin.  
     
     
         61 . The sized paper of  claim 53  wherein the sum of the mole percent of the quaternary diallyl ammonium monomers of formula IIIand the mole percent of the diallyl ammonium monomers of formula IV constitutes preferably at least 40% of monomers in the amphoteric promoter resin.  
     
     
         62 . The sized paper of  claim 53  wherein the monomers of the anionic unsaturated organic acid of formula IV is at least 33 mole % of the sum of monomers of the cationic quaternary diallyl ammonium monomer of formula (III) and cationic diallylammonium monomer of formula (IV)  
     
     
         63 . The sized paper of  claim 53  wherein the monomers of the anionic unsaturated organic acid of formula (IV) is at least 50 mole % of the sum of monomers of the cationic quaternary diallyl ammonium monomer of formula (III) and cationic diallylammonium monomer of formula (IV  
     
     
         64 . The sized paper of  claim 53  wherein the monomers of the anionic unsaturated organic acid of formula (IV) is at least 65 mole % of the sum of monomers of the cationic quaternary diallyl ammonium monomer of formula (III) and cationic diallylammonium monomer of formula (IV)  
     
     
         65 . The sized paper of  claim 53  wherein the monomers of the cationic diallylammonium monomer of formula (IV) constitutes up to 65% of sum of the monomers of the cationic quaternary diallyl ammonium monomer of formula (III) and cationic diallylammonium monomer of formula (IV)  
     
     
         66 . The sized paper of  claim 53  wherein the monomers of the cationic diallylammonium monomer of formula (IV) constitutes 10 to 50% of sum of the monomers of the cationic quaternary diallyl ammonium monomer of formula (III) and cationic diallylammonium monomer of formula (IV)  
     
     
         67 . A sized paper of  claim 53  wherein the sizing agent and amphoteric promoter resin are present in amounts sufficient to produced a sized paper containing from about 0.005 wt % to about 1.5 wt % of the sizing agent, and from about 0.002 wt % to about 0.6 wt % of the amphoteric promoter resin, based on the weight of the dried sized paper.  
     
     
         68 . A sized paper of  claim 53  wherein the sizing agent and amphoteric promoter resin are present in amounts sufficient to produced a sized paper containing from about 0.025 wt % to about 0.5 wt % of the sizing agent, and from about 0.007 wt % to about 0.3 wt % of the amphoteric promoter resin, based on the weight of the dried sized paper.  
     
     
         69 . A sized paper of  claim 53  wherein the sizing agent and amphoteric promoter resin are present in amount sufficient to produced a sized paper containing from about 0.05 wt % to about 0.25 wt % of the sizing agent, and from about 0.012 wt % to about 0.15 wt % of the amphoteric promoter resin, based on the weight of the dried sized paper.  
     
     
         70 . The sized paper of  claim 53  wherein optical brighteners are added in amounts sufficient to produce white paper containing up to 1.5 wt % of the optical brightener based on the weight of the dried sized paper.  
     
     
         71 . A sized paper of  claim 53  wherein the polymerization reaction product has a weight average molecular weight of at least about 10,000.  
     
     
         72 . A sized paper of  claim 53  wherein the polymerization reaction product has a weight average molecular weight of at least about 30,000.  
     
     
         73 . The sized paper of  claim 53  wherein the paper sizing agent is selected from the group consisting of ketene dimer, ketene multimer, acid anhydride, organic isocyanate and rosin.  
     
     
         74 . The sized paper of  claim 73  wherein the paper sizing agent is selected from the group consisting of alkyl ketene dimer, branched alkyl ketene dimer, alkenyl ketene dimer, alkyl ketene multimer and alkenyl ketene multimer.  
     
     
         75 . The sized paper of  claim 73  wherein the paper sizing agent is an alkenyl succinic acid anhydride sizing agent.  
     
     
         76 . The sized paper of  claim 73  wherein the paper sizing agent is selected from the group consisting of alkyl ketene dimer, branched alkyl ketene dimer, alkenyl ketene dimer, alkyl ketene multimer, alkenyl ketene multimer, alkenyl succinic acid anhydride, stearic anhydride, alkyl isocyanate, alkyl carbamoyl chloride, alkylated melamine, rosin, styrene acrylate and styrene maleic anhydride.