Polymer systems and cleaning compositions comprising same

• US 20040068051A1
• Filed: 09/12/2003
• Published: 04/08/2004
• Est. Priority Date: 09/12/2002
• Status: Active Grant

• Current Assignee: The Procter & Gamble Company
• Original Assignee: The Procter & Gamble Company
• Inventors: Scheibel, Jeffrey John, Sadlowski, Eugene Steven, Ortiz, Rafael, Metrot, Veronique Sylvie
• Granted Patent: US 7,163,985 B2
• Time in Patent Office: Days
• US Class Current: 525/54.1
• CPC Class Codes: C11D 3/37 Polymers polymeric surface-active agents C11D1/008; polysaccharides C11D3/222
• CPC Class Codes: C11D 3/3723 Polyamines or polyalkyleneimines
• CPC Class Codes: C11D 3/3746 Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
• CPC Class Codes: C11D 3/3757 (Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
• CPC Class Codes: C11D 3/3769 (Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
• CPC Class Codes: C11D 3/3788 Graft polymers

Abstract

The present invention relates to stable polymer systems comprising anionic and modified polyamine polymers. When such polymer systems are employed in cleaning compositions, such cleaning compositions exhibit unexpectedly improved anti-soil re-deposition and situs whitening capabilities.

Claims

1. ) A polymer system comprising:

A.) an anionic polymer selected from the group consisting of

(i) anionic polymers comprising;

a.) a first moiety derived from monoethylenically unsaturated C₃-C₈ monomers comprising at least one carboxylic acid group, salts of such monomers, and mixtures thereof; and

b.) a second moiety selected from the group consisting of;

(1) moieties derived from modified unsaturated monomers having the formulae R—

Y-L and R-Z wherein;

i.) R is selected from the group consisting of C(X)H═

C(R¹)—

wherein R¹ is H, or C₁-C₄ alkyl; and

X is H, CO₂H, or CO₂R₂ wherein R₂ is hydrogen, alkali metals, alkaline earth metals, ammonium and amine bases, saturated C₁-C₂₀ alkyl, C₆-C₁₂ aryl, and C₇-C₂₀ alkylaryl;

ii.) Y is selected from the group consisting of —

CH₂—

, —

CO₂—

, —

OCO—

, and —

CON(R^a)_, —

CH₂OCO—

;

wherein R^a is H or C₁-C₄ alkyl;

iii.) L is selected from the group consisting of hydrogen, alkali metals, alkaline earth metals, ammonium and amine bases, saturated C₁-C₂₀ alkyl, C₆-C₁₂ aryl, and C₇-C₂₀ alkylaryl; and

iv.) Z is selected from the group consisting of C₆-C₁₂ aryl and C₇-C₁₂ arylalkyl; and

(2) moieties having the formula J-G-D wherein;

i.) J is selected from the group consisting of C(X)H═

C(R₁)—

wherein R₁ is H, or C₁-C₄ alkyl;

X is H, CO₂H, or CO₂R₂ wherein R₂ is hydrogen, alkali metals, alkaline earth metals, ammonium and amine bases, saturated C₂-C₂₀ alkyl, C₆-C₁₂ aryl, C₇-C₂₀ alkylaryl;

ii.) G is selected from the group consisting of C₁-C₄ alkyl, —

O—

, —

CH₂O—

, —

CO₂—

.

iii.) D is selected from the group consisting of —

CH₂CH(OH)CH₂O(R³O)_dR₄;

—

CH₂CH[O(R³O)_dR⁴]CH₂OH;

—

CH₂CH(OH)CH₂NR⁵(R³O)_dR⁴;

—

CH₂CH[NR⁵(R³O)_dR⁴]CH₂OH, and mixtures thereof;

wherein

 

R³ is selected from the group consisting of ethylene, 1,2-propylene, 1,3-propylene, 1,2-butylene, 1,4-butylene, and mixtures thereof;

 

R⁴ is a capping unit selected from the group consisting of H, C₁-C₄ alkyl, C₆-C₁₂ aryl and C₇-C₂₀ alkylaryl;

 

R⁵ is selected from the group consisting of H, C₁-C₄ alkyl C₆-C₁₂ aryl and C₇-C₂₀ alkylaryl; and

 

subscript index d is an integer from 1 to 100.  

(ii) graft co-polymers comprising a first moiety derived from monoethylenically unsaturated C₃-C₈ monomers comprising at least one carboxylic acid group, salts of such monomers, and mixtures thereof, said first moieties being grafted onto a C₁-C₄ carbon polyalkylene oxide,

 

and mixtures thereof; and

B.) a modified polyamine polymer selected from the group consisting of

(i) modified polyamines having the formulae

V_(n+1)W_mY_nZ or V_(n-k+1)W_mY_nY′

_kZ

 

wherein m is an integer from 0 to about 400;

n is an integer from 0 to about 400;

k is less than or equal to n wherein

a.) V units are terminal units having the formula;

b.) W units are backbone units having the formula;

c.) Y and Y′

units are branching units having the formula;

 

and

d.) Z units are terminal units having the formula;

wherein;

R units are selected from the group consisting of C₂-C₁₂ alkylene, C₄-C₁₂ alkenylene, C₃-C₁₂ hydroxyalkylene, C₄-C₁₂ dihydroxy-alkylene, C₈-C₁₂ dialkylarylene, —

(R¹O)_xR¹—

, —

(R¹O)_xR⁵(OR¹)_x—

, —

(CH₂CH(OR²)CH₂O)_z—

(R¹O)_yR¹(OCH₂CH(OR²)CH₂)_w—

, —

C(O)(R⁴)_rC(O)—

, —

CH₂CH(OR²)CH₂—

, and mixtures thereof;

wherein

R¹ is C₂-C₃ alkylene and mixtures thereof;

R² is hydrogen, —

(R¹O)_xB, and mixtures thereof;

wherein at least one B is selected from the group consisting of —

(CH₂)_qSO₃M, —

(CH₂)_pCO₂M, —

(CH₂)_q(CHSO₃M)CH₂SO₃M, —

(CH₂)_q—

(CHSO₂M)CH₂SO₃M, —

(CH₂)_pPO₃M, —

PO₃M, and mixtures thereof, and any remaining B moieties are selected from the group consisting of hydrogen, C₁-C₆ alkyl, —

(CH₂)_q —

SO₃M, —

(CH₂)_pCO₂M, —

(CH₂)_q(CHSO₃M)CH₂SO₃M,—

(CH2)_q —

(CHSO₂M)CH₂SO₃M, —

(CH₂)_pPO₃M, —

PO₃M, and mixtures thereof;

R⁴ is C₁-C₁₂ alkylene, C₄-C₁₂ alkenylene, C₈-C₁₂ arylalkylene, C₆-C₁₀ arylene, and mixtures thereof;

R⁵ is C₁-C₁₂ alkylene, C₃-C₁₂ hydroxy-alkylene, C₄-C₁₂ dihydroxyalkylene, C₈-C₁₂ dialkylarylene, —

C(O)—

, —

C(O)NHR⁶NHC(O)—

, —

R¹(OR¹)—

,—

C(O)(R⁴)_rC(O)—

, —

CH₂CH(OH)CH₂—

, —

CH₂CH(OH)CH₂O(R¹O)_yR¹—

OCH₂CH(OH)CH₂—

, and mixtures thereof;

R⁶ is C₂-C₁₂ alkylene or C₆-C₁₂ arylene;

X is a water soluble anion;

provided at least one backbone nitrogen is quaternized or oxidized

E units are selected from the group consisting of hydrogen, C₁-C₂₂ alkyl, C₃-C₂₂ alkenyl, C₇-C₂₂ arylalkyl, C₂-C₂₂ hydroxyalkyl, —

(CH₂)_pCO₂M, —

(CH₂)_qSO₃M, —

CH(CH₂CO₂M)-CO₂M, —

(CH₂)_pPO₃M, —

(R¹O)_xB, —

C(O)R³, and mixtures thereof;

provided that when any E unit of a nitrogen is a hydrogen, said nitrogen is not also an N-oxide;

R¹ is C₂-C₃ alkylene and mixtures thereof;

R³ is C₁-C₁₈ alkyl, C₇-C₁₂ arylalkyl, C₇-C₁₂ alkyl substituted aryl, C₆-C₁₂ aryl, and mixtures thereof;

at least one B is selected from the group consisting of —

(CH₂)_q—

SO₃M, —

(CH₂)_pCO₂M, —

(CH₂)_q(CHSO₃M)CH₂SO₃M, —

(CH₂)_q—

(CHSO₂M)CH₂SO₃M, —

(CH₂)_pPO₃M, —

PO₃M, and mixtures thereof, and any remaining B moieties are selected from the group consisting of hydrogen, C₁-C₆ alkyl, (CH₂)_q—

SO₃M, —

(CH₂)_pCO₂M, —

(CH₂)_q(CHSO₃M)CH₂SO₃M, —

(CH₂)_q—

(CHSO₂M)CH₂SO₃M, —

(CH₂)_pPO₃M, —

PO₃M, and mixtures thereof;

M is hydrogen or a water soluble cation in sufficient amount to satisfy charge balance; and

wherein the values for the following indices are as follows;

subscript index p is an integer from 1 to 6;

subscript index q is an integer from 0 to 6;

subscript index r has the value of 0 or 1;

subscript index w has the value 0 or 1;

subscript index x is an integer from 1 to 100;

subscript index y is an integer from 0 to 100; and

subscript index z has the value 0 or 1.

(ii) modified polyamines having formula (I);

a.) R is C₆-C₂₀ linear or branched alkylene, and mixtures thereof;

b.) X is an anion present in sufficient amount to provide electronic neutrality;

c.) n and subscript index n have equal values and are integers from 0 to 4;

d.) R¹ is a capped polyalkyleneoxy unit having formula;

—

(R²O)_x—

R³

 

wherein R² is C₂-C₄ linear or branched alkylene, and mixtures thereof;

subscript index x has a value from about 1 to about 50;

at least one R³ moiety is an anionic capping unit, with the remaining R³ moieties being selected from the group comprising hydrogen, C₁-C₂₂ alkylenearyl, an anionic capping unit, a neutral capping unit, and mixtures thereof;

e.) at least one Q moiety, is a hydrophobic quaternizing unit selected from the group comprising C₇-C₃₀ substituted or unsubstituted alkylenearyl, and mixtures thereof, any remaining Q moieties are selected from the group comprising lone pairs of electrons on the unreacted nitrogens, hydrogen, C₁-C₃₀ substituted or unsubstituted linear or branched alkyl, or C₃-C₃₀ substituted or unsubstituted cycloalkyl, and mixtures thereof;

 

and mixtures thereof.

2. ) The polymer system of claim 1 wherein said modified polyamine polymer is selected from the group consisting of polymers having the following formulae:

3. ) A cleaning composition comprising the polymer system of claim 1

4. ) A method of cleaning a situs comprising contacting said situs, or a soiled portion thereof, with the cleaning composition of claim 3 or a diluted solution comprising the cleaning composition of claim 3 and then optionally washing, followed by optionally rinsing said situs.