# Patent

## Title
Fluorine-free trisiloxane surfactant compositions for use in coatings and printing ink compositions

## Abstract

The present invention relates to coating and printing ink compositions possessing silicone surfactants compositions comprising fluorine-free organomodified trisiloxanes which are resistant to hydrolysis between a pH of about 3 to a pH of about 12. The coatings and printing ink composition of the present invention exhibit enhanced wetting, flow and leveling properties.

## Background
FIELD OF THE INVENTION
The present invention relates to silicone surfactant compositions that exhibit resistance to hydrolysis over a wide pH range. More particularly, the present invention relates to coating and printing ink compositions containing silicone surfactants compositions comprising fluorine-free organomodified trisiloxanes which are resistant to hydrolysis between a pH of about 3 to a pH of about 12.
BACKGROUND OF THE INVENTION
The topical application of liquid compositions to the surfaces of both animate and inanimate objects to effect a desired change involve the processes of controlling wetting, spreading, flow, leveling, foaming, detergency, and the like. When used in aqueous solutions to improve the delivery of active ingredients to the surface being treated, trisiloxane type compounds have been found to be useful in enabling the control of these processes to achieve the desired effect. However, the trisiloxane compounds may only be used in a narrow pH range, ranging from a slightly acidic pH of 6 to a very mildly basic pH of 7.5. Outside this narrow pH range, the trisiloxane compounds are not stable to hydrolysis undergoing a rapid decomposition.
In recent years, there has been a move to waterborne coatings in place of solventborne coatings from the viewpoints of resource savings and environmental pollution. For example, waterborne coatings have been investigated for primer coatings, base coatings and top coatings for automobiles. This allows flow-and-leveling agents for waterborne coatings having higher functionality to be required. In order to meet this requirement, acryl base polymers, modified silicone oils and the like have so far been used as flow-and-leveling agents. However, a satisfactory wetting, flow-and-leveling property and an improvement in coating defects are not necessarily achieved with these conventional techniques in the fields requiring a high level of appearance for uses such as automobiles which have been researched in recent years. So either large concentrations of organic surfactants or specialty perfluoroalkyl functionalized surfactants with very low surface tension are added in order to obtain a good appearance. One of the issues with using very high concentrations of organic surfactants is the adverse effects that exerted on other properties of coatings such as layer-to-layer adhesive property in recoating or roughening the surfaces of the recoated films.
Conventional organic surfactants provide only an inadequate solution to the leveling problem in the case of coatings, and there is an urgent need for new surfactants which make it possible to produce absolutely smooth coating films. Alternatively, the specialty fluoro based surfactants are facing pressures from toxicological and bioaccumulation fronts. The U.S. Environmental Protection Agency (EPA) is proposing to tighten regulation of such perfluoroalkyl materials that have the potential of braking down into toxic perfluoroalkyl carboxylates, such as perfluorooctanoic acid (PFOA), and perfluoroalkyl sulfonates, including perfluorooctanyl sulfonate (PFOS). These substances are expected to bioaccumulate, persist in the environment, and are likely to be “highly toxic”. Also, studies suggest that perfluoroalkyl sulfonates and carboxylates may get released in the air when items made with certain fluoropolymers are burned in municipal waste incinerators
Accordingly, the identification of non-fluorinated surfactants that can avoid environmental and health concerns is of interest. The present invention also describes the utility and application of this novel fluorine free surfactant compositions to provide improved flow, leveling and wetting benefits.
SUMMARY OF THE INVENTION
The present invention provides a fluorine-free coating composition comprising:

    
    
        a) at least one silicone composition selected from the group consisting of:
    
    


i) a trisiloxane compound of the general formula:

M1D1M2 

wherein,

M1=(R1)(R2)(R3)SiO1/2 
M2=(R4)(R5)(R6)SiO1/2 
D1=(R7)(Z)SiO2/2 
where R1 is selected from a branched or linear hydrocarbon group consisting of 2 to 4 carbons, aryl, and an alkyl hydrocarbon group of 4 to 9 carbons containing aryl substituents of 6 to 20 carbon atoms; R2, R3 R4, R5, R6 and R7 are each independently selected from the group consisting of 1 to 4 carbon monovalent hydrocarbon radicals, aryl, and a hydrocarbon group of 4 to 9 carbons containing an aryl group; Z is an alkyleneoxide group of the general formula:
R8(C2H4O)a(C3H6O)b(C4H8O)cR9, where R8 is a linear or branched divalent hydrocarbon radical of 2, 3, 5, 6, 7, 8, or 9 carbon atoms; R9 is selected from the group consisting of H, monovalent hydrocarbon radicals of from 1 to 6 carbon atoms and acetyl the subscripts a, b and c are zero or positive and satisfy the following relationships:

2≦a+b+c≦20 with a≧2;

ii) a trisiloxane compound of the general formula:

M3D2M4 

wherein,

M3=(R10)(R11)(R12)SiO1/2 
M4=(R13)(R14)(R15)SiO1/2 
D2=(R16)(Z′)SiO2/2
where R10, R11, R12 R13, R14, R15 and R16 are each independently selected from the group consisting of 1 to 4 carbon monovalent hydrocarbon radicals, aryl, and an alkyl hydrocarbon group of 4 to 9 carbons containing an aryl substituents of 6 to 20 carbon atoms; Z′ is an alkylene oxide group of the general formula:
R17(C2H4O)d(C3H6O)e(C4H8O)fR18, where R17 is selected from a branched or linear divalent hydrocarbon radical of the general formula:

—C4H8O—(C2H4O)—

R18 is selected from the group consisting of H, monovalent hydrocarbon radicals of from 1 to 6 carbon atoms and acetyl the subscripts d, e and f are zero or positive and satisfy the following relationships:

2≦d+e+f≦20 with d≧2;

iii) a trisiloxane compound of the general formula:

M5D3M6 

wherein,

M5=(R19)(R20)(R21)SiO1/2 
M6=(R22)(R23)(R24)SiO1/2 
D3=(R25)(Z′′)SiO2/2 
where R19, R20, R21, R22, R23, and R24 are each independently selected from the group consisting of 1 to 4 carbon monovalent hydrocarbon radicals, aryl, and an alkyl hydrocarbon group of 4 to 9 carbons containing an aryl substituents of 6 to 20 carbon atoms, R25 is a linear or branched hydrocarbon radical of 2 to 4 carbons; Z′′ is an alkylene oxide group of the general formula:
R26(C2H4O)g(C3H6O)h(C4H8O)iR27, where R26 is a linear or branched divalent hydrocarbon radical of 2, 3, 5, 6, 7, 8, or 9 carbon atoms; R27 is selected from the group consisting of H, monovalent hydrocarbon radicals of from 1 to 6 carbon atoms and acetyl the subscripts g, h and i are zero or positive and satisfy the following relationships:

2≦g+h+i≦20 with g≧2; and

    
    
        b) at least one coating resin,

wherein the composition exhibits enhanced resistance to hydrolysis.

    
    


The present invention further provides a fluorine-free printing ink composition comprising:

    
    
        a) at least one silicone composition selected from the group consisting of:
    
    


i) a trisiloxane compound of the general formula:

M1D1M2 

wherein,

M1=(R1)(R2)(R3)SiO1/2 
M2=(R4)(R5)(R6)SiO1/2 
D1=(R7)(Z)SiO2/2 
where R1 is selected from a branched or linear hydrocarbon group consisting of 2 to 4 carbons, aryl, and an alkyl hydrocarbon group of 4 to 9 carbons containing aryl substituents of 6 to 20 carbon atoms; R2, R3 R4, R5, R6 and R7 are each independently selected from the group consisting of 1 to 4 carbon monovalent hydrocarbon radicals, aryl, and a hydrocarbon group of 4 to 9 carbons containing an aryl group; Z is an alkyleneoxide group of the general formula:
R8(C2H4O)a(C3H6O)b(C4H8O)cR9, where R8 is a linear or branched divalent hydrocarbon radical of 2, 3, 5, 6, 7, 8, or 9 carbon atoms; R9 is selected from the group consisting of H, monovalent hydrocarbon radicals of from 1 to 6 carbon atoms and acetyl the subscripts a, b and c are zero or positive and satisfy the following relationships:

2≦a+b+c≦20 with a≧2;

ii) a trisiloxane compound of the general formula:

M3D2M4 

wherein,

M3=(R10)(R11)(R12)SiO1/2 
M4=(R13)(R14)(R15)SiO1/2 
D2=(R16)(Z′)SiO2/2 
where R10, R11, R12 R13, R14, R15 and R16 are each independently selected from the group consisting of 1 to 4 carbon monovalent hydrocarbon radicals, aryl, and an alkyl hydrocarbon group of 4 to 9 carbons containing an aryl substituents of 6 to 20 carbon atoms; Z′ is an alkylene oxide group of the general formula:
R17(C2H4O)d(C3H6O)e(C4H8O)fR18, where R17 is selected from a branched or linear divalent hydrocarbon radical of the general formula:

—C4H8O—(C2H4O)—

R18 is selected from the group consisting of H, monovalent hydrocarbon radicals of from 1 to 6 carbon atoms and acetyl the subscripts d, e and f are zero or positive and satisfy the following relationships:

2≦d+e+f≦20 with d≧2;

iii) a trisiloxane compound of the general formula:

M5D3M6 

wherein,

M5=(R19)(R20)(R21)SiO1/2 
M6=(R22)(R23)(R24)SiO1/2 
D3=(R25)(Z′′)SiO2/2 
where R19, R20, R21, R22, R23, and R24 are each independently selected from the group consisting of 1 to 4 carbon monovalent hydrocarbon radicals, aryl, and an alkyl hydrocarbon group of 4 to 9 carbons containing an aryl substituents of 6 to 20 carbon atoms, R25 is a linear or branched hydrocarbon radical of 2 to 4 carbons; Z′′ is an alkylene oxide group of the general formula:
R26(C2H4O)g(C3H6O)h(C4H8O)iR27, where R26 is a linear or branched divalent hydrocarbon radical of 2, 3, 5, 6, 7, 8, or 9 carbon atoms; R27 is selected from the group consisting of H, monovalent hydrocarbon radicals of from 1 to 6 carbon atoms and acetyl the subscripts g, h and i are zero or positive and satisfy the following relationships:

2≦g+h+i≦20 with g≧2; and

    
    
        b) at least one printing ink resin,

wherein the composition exhibits enhanced resistance to hydrolysis.

    
    


The coating and printing ink compositions of the present invention exhibit enhanced wetting, leveling and flow.



BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 displays a surface coated with a coating formulation presented in Table 12 which contains 1% Comparative Example OPE surfactant.
FIG. 2 displays a surface coated with a coating formulation presented in Table 12 which contains 1% Example 3 surfactant.
FIG. 3 displays a surface coated with a coating formulation presented in Table 12 which contains 0.25% Example 3 surfactant.
FIG. 4 displays a surface coated with a coating formulation presented in Table 13 which contains 1% Example 3 surfactant.
FIG. 5 displays a surface coated with a coating formulation presented in Table 13 which contains 0% surfactant.
FIG. 6 displays surface coated with a coating formulation presented in Table 13 which contains 1% Comparative Example OPE surfactant.



DETAILED DESCRIPTION OF THE INVENTION
As used herein, integer values of stoichiometric subscripts refer to molecular species and non-integer values of stoichiometric subscripts refer to a mixture of molecular species on a molecular weight average basis, a number average basis or a mole fraction basis.
The present invention provides coating and printing ink compositions comprising at least one silicone composition selected from the group consisting of a trisiloxane compounds having the general formula (i), (ii), and (iii).
Trisiloxane compound (i) has the formula:

M1D1M2 

wherein,

M1=(R1)(R2)(R3)SiO1/2 
M2=(R4)(R5)(R6)SiO1/2 
D1=(R7)(Z)SiO2/2 
where R1 is selected from a branched or linear hydrocarbon group consisting of 2 to 4 carbons, aryl, and an alkyl hydrocarbon group of 4 to 9 carbons containing an aryl substituents of 6 to 20 carbon atoms; R2, R3 R4, R5, R6 and R7 are each independently selected from the group consisting of 1 to 4 carbon monovalent hydrocarbon radicals, aryl, and a hydrocarbon group of 4 to 9 carbons containing an aryl group. Z is an alkyleneoxide group of the general formula:
R8(C2H4O)a(C3H6O)b(C4H8O)cR9, where R8 is a linear or branched divalent hydrocarbon radical of 2, 3, 5, 6, 7, 8, or 9 carbon atoms; R9 is selected from the group consisting of H, monovalent hydrocarbon radicals of from 1 to 6 carbon atoms and acetyl the subscripts a, b and c are zero or positive and satisfy the following relationships:

2≦a+b+c≦20 with a≧2.

When the subscript a satisfies the condition 2≦a≦5 it is advisable to utilize a co-surfactant as hereinafter set forth in order to obtain the benefit of the compositions of the present invention
Trisiloxane compound (ii) has the formula:

M3D2M4 

wherein

M3=(R10)(R11)(R12)SiO1/2 
M4=(R13)(R14)(R15)SiO1/2 
D2=(R16)(Z′)SiO2/2 
where R10, R11, R12 R13, R14, R15 and R16 are each independently selected from the group consisting of 1 to 4 carbon monovalent hydrocarbon radicals, aryl, and an alkyl hydrocarbon group of 4 to 9 carbons containing an aryl substituents of 6 to 20 carbon atoms; Z′ is an alkylene oxide group of the general formula:
R17(C2H4O)d(C3H6O)e(C4H8O)fR18, where R17 has the formula:

—C4H8O—(C2H4O)—

R18 is selected from the group consisting of H, monovalent hydrocarbon radicals of from 1 to 6 carbon atoms and acetyl the subscripts d, e and f are zero or positive and satisfy the following relationships:

2≦d+e+f≦20 with d≧2.

When the subscript d satisfies the condition 2≦d≦5 it is advisable to utilize a co-surfactant as hereinafter set forth in order to obtain the benefit of the compositions of the present invention.
Trisiloxane compound (iii) has the formula:

M5D3M6 

wherein

M5=(R19)(R20)(R21)SiO1/2 
M6=(R22)(R23)(R24)SiO1/2 
D3=(R25)(Z′′)SiO2/2 
where
R19, R20, R21, R22, R23, and R24 are each independently selected from the group consisting of 1 to 4 carbon monovalent hydrocarbon radicals, aryl, and an alkyl hydrocarbon group of 4 to 9 carbons containing an aryl substituents of 6 to 20 carbon atoms, R25 is a linear or branched hydrocarbon radical of 2 to 4 carbons; Z′′ is an alkylene oxide group of the general formula:
R26(C2H4O)g(C3H6O)h(C4H8O)iR27, where R26 is a linear or branched divalent hydrocarbon radical of 2, 3, 5, 6, 7, 8, or 9 carbon atoms;
R27 is selected from the group consisting of H, monovalent hydrocarbon radicals of from 1 to 6 carbon atoms and acetyl the subscripts g, h and i are zero or positive and satisfy the following relationships:

2≦g+h+i≦20 with g≧2.

When the subscript g satisfies the condition 2≦g≦5 it is advisable to utilize a co-surfactant as hereinafter set forth in order to obtain the benefit of the compositions of the present invention.
One method of producing the composition of the present invention is to react a molecule of the following formula:

MDHM

where DH is the hydride precursor to the D′ structural unit in the composition of the present invention, wherein the definitions and relationships are later defined and consistent with those defined above, under hydrosilylation conditions, with an olefinically modified polyalkyleneoxide, such as allyloxypolyethyleneglycol, or methallyloxypolyalkyleneoxide, which are incorporated here as examples, and not set forth to limit other possible olefinically modified alkyleneoxide components. As use herein the phrase “olefinically modified polyalkyleneoxide” is defined as a molecule possessing one or more alkyleneoxide groups containing one or more, terminal or pendant, carbon-carbon double bonds. The polyether (the precursor to the substituents Z, Z′ or Z′′) is an olefinically modified polyalkyleneoxide (hereinafter referred to as “polyether”) is described by the general formula:

CH2═CH(R28)(R29)jO(R30)k(C2H4O)m(C3H6O)n(C4H8O)pR31 

where R28 is H or methyl; R29 is a divalent alkyl radical of 1 to 6 carbons where the subscript j may be 0 or 1; R30 is —C2H4O—, where the subscript k may be 0 or 1; R31 is H, a monofunctional hydrocarbon radical of 1 to 6 carbons, or acetyl and the subscripts m, n and p are zero or positive and satisfy the relationship 2≦m+n+p≦20 with m≧2. When the polyether is composed of mixed oxyalkyleneoxide groups (i.e. oxyethylene, oxypropylene and oxybutylene) the units may be blocked, or randomly distributed. One skilled in the art will understand the advantages of using a blocked or random configuration. Illustrative examples of blocked configurations are: -(oxyethylene)a(oxypropylene)b-; -(oxybutylene)c(oxyethylene)a-; and -(oxypropylene)b(oxyethylene)a(oxybutylene)c-.

Illustrative examples of the polyether are provided below, but not limited to:
CH2═CHCH2O(CH2CH2O)8H; CH2═CHCH2O(CH2CH2O)8CH3;
CH2═CHCH2O(CH2CH2O)4(CH2CH(CH3)O)5H;
CH2═CHO(CH2CH2O)5(CH2CH(CH3)O)5H;
CH2═C(CH3)CH2O(CH2CH2O)4(CH2CH(CH3)O)5C(═O)CH3;
CH2═CHCH2O(CH2CH2O)5(CH2CH(CH3)O)2(CH2CH(CH2CH3)O)2H
Polyether modified siloxanes are prepared in the normal manner through the use of a hydrosilylation reaction to graft the olefinically modified (i.e. vinyl, allyl or methallyl)polyalkyleneoxide onto the hydride (SiH) intermediate of the trisiloxane of the present invention.
In one embodiment of the invention, the trisiloxane compound of formula (i), R1 and R4 are selected from a branched or linear hydrocarbon group consisting of 2 to 4 carbons, aryl, an alkyl hydrocarbon group of 4 to 9 carbons containing an aryl substituents of 6 to 20 carbon atoms; in another embodiment, R1 and R4 are 3 to 4 carbons or aryl. R2, R3, R5, R6 and R7 are each independently selected from the group consisting of 1 to 4 carbon monovalent hydrocarbon radicals, aryl, and a hydrocarbon group of 4 to 9 carbons containing an aryl group; in another embodiment, R2, R3, R5, R6 and R7 are 1 to 2 carbon monohydrocarbon radicals and aryl; and in one specific embodiment of the invention, R2, R3, R5, R6 and R7 methyl. Z is an alkyleneoxide group of the general formula: R8(C2H4O)a(C3H6O)b(C4H8O)cR9, where R8 is a linear or branched divalent hydrocarbon radical of 2, 3, 5, 6, 7, 8, or 9 carbon atoms, more preferably 3 to 7 carbons; most preferably 3 to 6 carbons. Subscripts a, b and c are zero or positive and satisfy the following relationships: 2≦a+b+c≦20 with a≧2; preferably a is 5 to 20, more preferably 5 to 8; preferably b is 0 to 10; more preferably 0 to 5; preferably c is 0 to 8, more preferably 0 to 4. R9 is selected from the group consisting of H, monovalent hydrocarbon radicals of from 1 to 6 carbon atoms and acetyl.
In another embodiment of the invention, the trisiloxane compound formula (i), R1, R4 and R7 are selected from a branched or linear hydrocarbon group consisting of 2 to 4 carbons, and aryl; in another embodiment, R1, R4 and R7 are 3 to 4 carbons. R2, R3, R5 and R6 are each independently selected from the group consisting of 1 to 4 carbon monovalent hydrocarbon radicals, and aryl; in yet another embodiment, R2, R3, R5 and R6 are 1 to 2 carbons; and in yet another embodiment, R2, R3, R5 and R6 are methyl. Z is as described above.
According to one embodiment of the invention, the trisiloxane compound formula (ii), R10, R11, R12 R13, R14, R15 and R16 are each independently selected from the group consisting of 1 to 4 carbon monovalent hydrocarbon radicals, and aryl; Z′ is an alkylene oxide group of the general formula: R17(C2H4O)d(C3H6O)e(C4H8O)fR18, where R17 is selected from a branched or linear divalent hydrocarbon radical of the general formula:

—C4H8O—(C2H4O)—

R18 is selected from the group consisting of H, monovalent hydrocarbon radicals of from 1 to 6 carbon atoms and acetyl; in one specific embodiment, R18 is H, and monovalent hydrocarbon radicals of from 1 to 4 carbon atoms; the subscripts d, e and f are zero or positive and satisfy the following relationships:

2≦d+e+f≦20 with d≧2;

preferably d is 5 to 20, more preferably 5 to 8; preferably e is 0 to 10; more preferably 0 to 5; preferably f is 0 to 8, more preferably 0 to 4.

In one embodiment of the invention, the trisiloxane compound formula (iii), R19, R20, R21, R22, R23, and R24 are each independently selected from the group consisting of 1 to 4 carbon monovalent hydrocarbon radicals and aryl; R25 is a linear or branched hydrocarbon radical of 2 to 4 carbons; in another embodiment, R25 is a linear or branched hydrocarbon radical of 3 to 4 carbons; Z′′ is an alkylene oxide group of the general formula: R26 (C2H4O)g(C3H6O)h(C4H8O)iR27, where R26 is a linear or branched divalent hydrocarbon radical of 2, 3, 5, 6, 7, 8, or 9 carbon atoms; in another embodiment, R26 is a linear or branched divalent hydrocarbon radical of 3 to 7 carbons; in another embodiment, R26 is a linear or branched divalent hydrocarbon radical of 3 to 6 carbons.
R27 is selected from the group consisting of H, monovalent hydrocarbon radicals of from 1 to 6 carbon atoms and acetyl; more preferably H, and monovalent hydrocarbon radicals of from 1 to 4 carbon atoms; the subscripts g, h and i are zero or positive and satisfy the following relationships: 2≦g+h+i≦20 with g≧2; preferably g is 5 to 20, more preferably 5 to 8; preferably h is 0 to 10; more preferably 0 to 5; preferably i is 0 to 8, more preferably 0 to 4.
Precious metal catalysts suitable for making polyether-substituted siloxanes are also well known in the art and comprise complexes of rhodium, ruthenium, palladium, osmium, iridium, or platinum. Many types of platinum catalysts for this SiH olefin addition reaction are known and such platinum catalysts may be used to generate the compositions of the present invention. The platinum compound can be selected from those having the formula (PtCl2Olefin) and H(PtCl3Olefin) as described in U.S. Pat. No. 3,159,601, hereby incorporated by reference. A further platinum containing material can be a complex of chloroplatinic acid with up to 2 moles per gram of platinum of a member selected from the class consisting of alcohols, ethers, aldehydes and mixtures thereof as described in U.S. Pat. No. 3,220,972 hereby incorporated by reference. Yet another group of platinum containing materials useful in this present invention is described in U.S. Pat. Nos. 3,715,334; 3,775,452 and 3,814,730 (Karstedt). Additional background concerning the art may be found in J. L. Spier, “Homogeneous Catalysis of Hydrosilation by Transition Metals”, in Advances in Organometallic Chemistry, volume 17, pages 407 through 447, F. G. A. Stone and R. West editors, published by Academic Press (New York, 1979). Those skilled in the art can easily determine an effective amount of platinum catalyst. Generally an effective amount ranges from about 0.1 to 50 parts per million of the total organomodified trisiloxane composition.
The coating and printing ink compositions as well as the siloxanes of the present invention exhibit an enhanced resistance to hydrolysis outside a pH range ranging from 6 to 7.5, i.e. in extreme environmental. conditions. An extreme environment is defined as an aqueous solution pH below 6 or above 7.5 or non-aqueous equivalents in terms of Bronsted acidity or basicity or Lewis acidity ort basicity. Enhanced resistance to hydrolysis can be demonstrated by a variety of tests but as used herein enhanced resistance to hydrolysis means 50 mole percent or more of the hydrolysis resistant composition of the present invention remains unchanged or unreacted after a period of a twenty-four hour exposure to aqueous acidic conditions where the solution has a pH lower than 6 or after a period of a twenty-four hour exposure to aqueous basic conditions where the solution has a pH greater than 7.5. Under acidic conditions the compositions of the present invention show a survival of 50 mole percent of the original concentration or greater at a pH of 5 or less for a period of time in excess of 48 hours; specifically the compositions of the present invention show a survival of 50 mole percent or greater at a pH of 5 or less for a period of time in excess of 2 weeks; more specifically the compositions of the present invention show a survival of 50 mole percent or greater at a pH of 5 or less for a period of time in excess of 1 month; and most specifically the compositions of the present invention show a survival of 50 mole percent or greater at a pH of 5 or less for a period of time in excess of 6 months. Under basic conditions the compositions of the present invention show a survival of 50 mole percent or greater at a pH of 8 or more for a period of time in excess of 2 weeks; specifically the compositions of the present invention show a survival of 50 mole percent or greater at a pH of 8 or more for a period of time in excess of 4 weeks; more specifically the compositions of the present invention show a survival of 50 mole percent or greater at a pH of 8 or more for a period of time in excess of 6 months; and most specifically the compositions of the present invention show a survival of 50 mole percent or greater at a pH of 8 or more for a period of time in excess of 1 year.
The coating and printing ink compositions of the present invention may be utilized in a variety of forms: as liquid solutions, dispersions of solids in liquids, dispersions of liquids in liquids as the previously described emulsions, solid mixtures or solid solutions either separately or in the forms previously listed in combination one with the other.
a. Coatings:
Typically coatings formulations will require a wetting agent or surfactant for the purpose of emulsification, compatibilization of components, leveling, flow and reduction of surface defects. Additionally, these additives may provide improvements in the cured or dry film, such as improved abrasion resistance, antiblocking, hydrophilic, and hydrophobic properties. Coatings formulations may exist as solventborne coatings, waterborne coatings, high solids, neat and powder coatings.
The term “leveling” as defined herein is understood to refer to the ability of the applied coating to form a smooth film in which imperfections left by the applicator, such as a brush or roller, disappear during the drying process. The term “flow” as defined herein refers to the spreadability of the coating and to the ease with which the coating can be applied. The term “wetting” as described herein is the ability of a formulation to wet the surfaces of substrates efficiently without pin-holes and defects.
Paint surfaces are normally not entirely smooth but instead have a more or less structured surface referred to as waviness or else as orange peel. These surfaces may be finely structured, with a short wave, or coarsely structured, with a long wave. In the majority of cases, this waviness is unwanted and a surfactant is necessary to provide flow, leveling and wetting to achieve a surface which is in any way smooth.
The coatings compositions of the present invention can be employed as: architecture coatings for both interior and exterior applications; original equipment manufacturer (OEM) product coatings or finishes for automotive, marine, aircraft, a variety of land transportation, appliances, metal furniture, machinery and equipment, coil, metal containers, insulating varnishes, pipe, packaging, overprint, release, prefinished wood, wood furniture, plastic substrates, scratch off coatings, nonstick cookware, acoustic ceiling tiles, fiber sizing and general metal; Special Purpose coatings such as industrial maintenance coatings, automotive refinish, traffic paints and miscellaneous coatings such as roof, tank, deck coatings, masonry coatings, masonry water repellent and concrete cure and seal coatings, and the like.
Typical coating resin types include but is not limited to polyesters, alkyds, acrylics, epoxies, polyurethanes, chlorinated polyolefins, polyvinylidene fluoride, urethane-polyester copolymers, styrene-butadiene, acrylic-urethane copolymers, PVC, epoxy esters, epoxy-aminos, epoxy-phenolic, phenolic, styrene-acrylic, epoxy acrylic, urethane-acrylic, silicone, acrylic-polyesters, epoxy-polyamide, fluoropolymer, polyvinyl acetate, vinyl-acrylic, silicone-acrylic, vinyl acetate-ethylene, styrene-acrylic, asphalt, coal tar, styrene butadiene, hydrocarbon, vinyl acetate-acrylic and silane systems, and mixtures copolymers and terpolymers thereof in amount know and conventional in the art.
Accordingly, an object of the present invention is to provide novel trisiloxane surfactants capable of being utilized for uses that requires a high level of aesthetics and appearance and that does not have disadvantages associated perfluorinated surfactants while providing increased resistance to hydrolysis.
Coating Additives:
Buffers, preservatives and other standard additives as known in the art can be included in the coating composition of the invention in known and conventional amounts.
Solvents can be included in coating compositions of the present invention. Typically, the solvents are in a liquid state at room temperature. Suitable solvents include water, alcohols, aromatic solvents, oils (i.e. mineral oil, vegetable oil, silicone oil, and the like), lower alkyl esters of vegetable oils, fatty acids, ketones, glycols, polyethylene glycols, diols, paraffinics, and the like. In one specific embodiment of the invention, the solvent is selected from the group consisting of 2,2,4-trimethyl, 1-3-pentane diol, n-methyl-pyrrolidone and alkoxylated (especially ethoxylated) versions thereof as illustrated in U.S. Pat. No. 5,674,832, incorporated by reference herein.
Co-Surfactants:
Co-surfactants can be included in the coating compositions of the present invention. According to one embodiment of the invention, typical co-surfactants include nonionic, cationic, anionic, amphoteric, zwitterionic, polymeric surfactants, or any mixture thereof. The co-surfactants are typically hydrocarbon based, silicone based or fluorocarbon based.
Moreover, other co-surfactants, that have short chain hydrophobes that do not interfere with superspreading as described in U.S. Pat. No. 5,558,806, incorporated by reference herein, are also useful.
Other useful co-surfactants include alkoxylates, especially ethoxylates, containing block copolymers including copolymers of ethylene oxide, propylene oxide, butylene oxide, and mixtures thereof; alkylarylalkoxylates, especially ethoxylates or propoxylates and their derivatives including alkyl phenol ethoxylate; arylarylalkoxylates, especially ethoxylates or propoxylates. and their derivatives; amine alkoxylates, especially amine ethoxylates; fatty acid alkoxylates; fatty alcohol alkoxylates; alkyl sulfonates; alkyl benzene and alkyl naphthalene sulfonates; sulfated fatty alcohols, amines or acid amides; acid esters of sodium isethionate; esters of sodium sulfosuccinate; sulfated or sulfonated fatty acid esters; petroleum sulfonates; N-acyl sarcosinates; alkyl polyglycosides; alkyl ethoxylated amines; and so forth.
In one embodiment of the invention, the amount of co-surfactant employed in the coating composition ranges from about 0.01 to about 5 weight percent of the total composition. In another embodiment of the invention, the amount of co-surfactant employed in the coating composition ranges from about 0.05 to about 2 weight percent of the total composition. In yet another embodiment of the invention, the amount of co-surfactant employed in the coating composition ranges from about 0.01 to 1 weight percent of the total composition.
Specific examples of co-surfactants include alkyl acetylenic diols (SURFONYL-Air Products), pyrrolidone based surfactants (e.g., SURFADONE-LP 100-ISP), 2-ethyl hexyl sulfate, isodecyl alcohol ethoxylates (e.g., RHODASURF DA 530-Rhodia), ethylene diamine alkoxylates (TETRONICS-BASF), ethylene oxide/propylene oxide copolymers (PLURONICS-BASF), Gemini type surfactants (Rhodia) and diphenyl ether Gemini type surfactants (e.g. DOWFAX-Dow Chemical).
In a specific embodiment of the invention, the co-surfactant is at least one selected from the group consisting of ethylene oxide/propylene oxide copolymers (EO/PO); amine ethoxylates; alkyl polyglycosides; and oxo-tridecyl alcohol ethoxylates.
The fluorine-free trisiloxane surfactants of the invention, as more fully described herein above, are used in the coating formulations in relatively small amounts. In one embodiment of the invention, the amount of silicone surfactant employed in the coating composition ranges from about 0.01 to about 5 weight percent of the total composition. In another embodiment of the invention, the amount of silicone surfactant employed in the coating composition ranges from about 0.05 to about 2 weight percent of the total composition. In yet another embodiment of the invention, the amount of silicone surfactant employed in the coating composition ranges from about 0.01 to 1 weight percent of the total composition.
The surfactants of the invention can be used as solutions, emulsions or 100% substances, depending on the nature and mode of application of the coating material.
b. Printing Inks
Printings inks and graphic arts products are homogeneous products which consist of pigments, dyes or any kind of coloring matter that can be used to provide aesthetic or functions to printed materials. These functions include visibility, rheology, light fastness and few other parameters useful for product identification or protection. Pigments will be treated in order to be sustained in homogeneous form that will allow their transfer from liquid to solid with appropriate printing equipments. To do so vehicles constituted of binders and solvents will be used to provide the necessary flow to the ink composition. The printing technologies used will affect the possible use of binders and solvents used to manufacture the ink.
The inks technologies can be divided broadly into the following categories: lithographic process (to which belong lithography and offset technologies); typographic process (to which belong flexography) or gravure process (to which belong gravure technologies); and Non Impact Process and Digital Imaging systems which are new emerging technologies applied in particular in computerized edition. It is noticeable that in all the processes involved one of the most critical issue is the transfer from a liquid ink to solid state onto substrate of various nature that have very different surface activities. Thus, in all the printing inks systems surface activity of the liquid and solids is an important part of the quality of printing.
In liquid inks, applied by either flexographic or gravure processes, the ink technologies can be quite similar in terms of composition and will mainly differ by the specifications of inks in terms of viscosity, solvent type, pigment concentration and other parameters induced by the end use application.
Liquid inks can be divided into solventborne (SB), radical curing (UV) or water based systems (WB).
The nature of the solvent used will obviously affect the binder and polymer selection used to design the inks. In SB systems low boiling point alcohols and esters will be used. The type of resins used are therefore selected to be soluble in these solvents The most common grades are nitrocellulosic, polyurethanes, acrylics soluble, polyamides, ketonic or maleic resins, polyvinyl chlorides, epoxies, isocyanates, polyvinyl butyral and the like.
In WB systems, solvent being mainly water, the resins have to be designed in a way that they can be diluted or soluble in water but once applied should be resistant to water and humidity. This apparent contradiction has been overcome by use of anionic (or cationic) based polymers that have the ability to release and loose or block their hydrophilic or hydrosoluble moiety upon drying. Also curing polymers are used based on non ionic polymer cured with appropriate curing agents like isocyanates or epoxys or melamines. Typical products used in this area include acrylic and styrene acrylic emulsions or latexes, polyurethane dispersions, epoxy dispersions, polyacrylates, polyvinylic dispersions, soluble polyamides or maleic resins and the like.
UV inks typically do not contain solvents but are mainly constituted of low molecular weight polymers or oligomers diluted with monomers when necessary. The different components are selected to be cured under radical polymerization upon exciting with UV lamps in association with photo initiators. Typical polymers include acrylates, epoxy acrylates, urethane acrylates, polyesters acrylates and their relative monomers bearing unsaturations.
Pigments, thickeners and other standard additives as known in the art can be included in the printing ink composition of the invention in known and conventional amounts.
In liquid inks the pigments, fillers or particulates giving the visual aspect of the inks have to be very well dispersed and grinded in order to reach appropriate flow and leveling on the substrates and during transfer from the press. To do so surface active dispersing agents or binders acting as polymeric dispersants are used. Specific grades of the resins mentioned above have the ability to properly disperse and sustain pigments in the appropriate form. Surface-active agents of many different natures are also used to disperse pigments. We can also find anionic dispersants like alkyl phosphates, sulphonates or sulfates and the like), cationic dispersant (like quaternary ammoniums), amphoteric dispersant (like betaines, or alkyl ethoxylates (like formerly used nonyl phenol ethoxylate, alcohol ethoxylates and the like), polyether siloxane (Like EO/PO modified silicones). Because of their chemical structure and the electrostatic method of stabilization of the pigment particles, surfactants may cause different defects: Water sensitivity, Foam formation, Interference with intercoat adhesion. The use of appropriate surface-active agents to compensate or minimize these defects becomes then almost mandatory in many applications.
Beside the pigments dispersion, other ingredients are used to finalize the properties required by the ink; transfer from printing unit, wetting of substrates, adhesion, specific resistances (like thermal or chemical resistances) or properties (like gloss). Typical formulation usually comprises several polymer systems providing different effects, and it is not rare to see complex formulation with more three or four different binders. The binders listed above are again involved to different extents depending on their individual contributions to the required properties.
Beside the binders additional ingredients will be provided that have other functions. Among these, defoamers (active to reduce foam) or antifoam (active to prevent foam formation) are very important classes. This in particular true for WB system were surface tension of the main solvent is the main responsible for foam generation. Silicone based and non silicone based defoamers are very often described. The silicone based defoamers consist of either emulsion forms or pure silicone and modified silicone oil in water together or not with silica particles or pure or emulsion forms of so called polyether siloxane based material. Silicones are sometimes viewed as critical in printing inks due to their high efficiency which can lead to multiple drawbacks among which fishe eyes is the most critical one. Non silicone based defoamers consist mainly of mineral oil based material and non mineral based material emulsified or not together with hydrophobic solids.
Though necessary, defoamers tend to create leveling and wettability problems that other additives known as wetting agents or spreaders will tend to minimize or suppress. Typical leveling and wetting agents include also silicone based and non silicone based surfactants. Typical non silicone based material include diethylenic surfactants, specific alkyl and alkyl aryl ethoxylates and fluoro carbon based surfactants are particularly effective. One of the issues with the typical silicone surfactant is its hydrolytic instability outside neutral pH conditions. Since most of the ink formulations have a pH on the basic side (pH 7-10), the surfactant compositions of the present invention are very useful in printing ink formulations.
Beside defoamers typical printing inks will also contain ingredients that can reduce or adjust coefficient of friction (COF). Here again we can differentiate silicone based additives and non silicone based additives. The non silicone based additives are natural, chemical or petroleum derivatives like natural waxes, (carnauba waxes and the like), olefinic waxes (PE or PP waxes), fluorinated waxes (PTFE), chemical waxes (amides). Other additives may include plasticizers (like phatlates, phosphates), glycols and coalescing agents.
Glycols and coalescing agents are also involved when WB inks are designed to modify film formation temperature or drying speed. Among these we can discriminate; Oxide-based glycol ether solvents (like Ethylene glycol monomethyl ether, Ethylene glycol monoethyl ether, Ethylene glycol monopropyl ether, Butyl carbitol, Dipropylene glycol dimethyl ether, butyl glycol, butyldiglycol) and Esters based solvents like (Ethylene glycol monobutyl ether acetate, Diethylene glycol monoethyl ether acetate, methoxypropylacetate, Butyl cellosolve acetate).
Another important ingredient almost always present in inks is adhesion promoter. The nature of some substrates sometimes require special additives that can enhance the adhesion of printing inks on them. Among these the most classical known products are chelates of titanates (like titanium acetyl acetonate) or zirconium (like zirconium carbonates or propionates), zinc oxides solutions, polyaziridines (though carcinogenic materials), organofunctional silanes (like Epoxy silane Silquest A-187 or A-1871, amino silane Silquest A-1120), imines (like polyethylene imine). Numerous other additives may include also optical brighteners, humectants (urea or phenols based material to avoid skin drying), UV absorbers (for light stability), rheological agents (thixotropic or sag reducing agents, thickeners), amines (for pH adjustments), biocides and so on.
A typical WB formulation is as follows: Organic pigment dispersion made with surfactant or acrylic solution resin in water; Polymer emulsion (stryene acrylic or urethane dispersion); Acrylic solution resin; PE wax dispersion; Silicone based antifoam; Non silicone based antifoam; Wetting agent; Thixotropic agent; Thickener; Coalescing agent; Alcohol; and Water.
EXAMPLES
The invention is illustrated by the following non-limiting examples:
The hydride intermediates for the organomodified trisiloxane surfactant compositions of the present invention were prepared as follows.
Preparation of Intermediate Example 1
1,5-di(t-butyl)-1,1,3,5,5,Pentamethyltrisiloxane (See Structure 1)
100 g tBuMe2SiCl and 46 g MeHSiCl2 were dissolved in 150 ml isopropylether (IPE) and placed in an addition funnel. 150 g water and 250 ml IPE were charged into a 1 L round bottom flask equipped with a mechanical stirrer, reflux condenser and N2 inlet. The chlorosilanes were added dropwise via the addition funnel at room temperature (23° C.) over a period of 1 h. After addition was completed, the temperature was adjusted to 70° C. and the reaction was run at reflux temperature for 20 h and progress followed by GC (88% yield at 20 h). When the reaction was finished, the water was drained off via a separation funnel. The fluid was washed 3 times using 100 g of water each time. 25 g of NaHCO3 was mixed with 100 g of water and added slowly to the mixture and stirred for 30 min. The water was again drained and dried over sodium sulfate. After filtering, the IPE was stripped off on the rotor evaporator and the crude product was further fractional distilled under reduced pressure to afford 63 g tBuMe2SiOMe(H)SiOSi Me2tBu (GC purity 97%).
Reaction sequence for preparation of hydride intermediate;
2tBuMe2SiCl+MeHSiCl2 H2O/IPE tBuMe2SiOMe(H)SiOSiMe2tBu




Preparation of Intermediate Example 2
1,5-di(isopropyl)-1,1,3,5,5,Pentamethyltrisiloxane (See Structure 2)
25 g iPrMe2SiCl (0.183 moles) and 13.1 g MeHSiCl2 (0.114 moles) were dissolved in 80 ml isopropylether (IPE) and placed in an addition funnel. 50 g water and 100 ml IPE were charged into a 500 ml round bottom flask equipped with a mechanical stirrer, reflux condenser and N2 inlet. The chlorosilanes were added dropwise via the addition funnel at room temperature (23° C.) over a period of 40 min. After addition was completed, the temperature was adjusted to 80° C. and the reaction was run at reflux temperature for 4 h and progress followed by GC (75% yield at 4 h). When the reaction was finished, the water was drained off via a separation funnel. The fluid was washed 3 times using 80 g of water each time. 25 g of NaHCO3 was mixed with 100 g of water and added slowly to the mixture and stirred for 30 min. The water was again drained and dried over sodium sulfate. After filtering, the IPE was stripped off on the rotor evaporator and the crude product was further fractional distilled under reduced pressure to afford 10 g iPrMe2SiOMe(H)SiOSi Me2iPr (GC purity 93%).
Reaction sequence for preparation of hydride intermediate
2iPrMe2SiCl+MeHSiCl2 H2O/IPE iPrMe2SiOMe(H)SiOSiMe2iPr




Preparation of Examples
Hydride Intermediate Examples 1 and 2 were further modified with various allylpolyalkyleneoxides to yield the organomodified trisiloxane surfactant compositions of Examples 1 and 2 and Example 3 was prepared with hydride Intermediate Example 3 as presented in Table 1, as well as the Comparative Example trisiloxane surfactants displayed in Table 2.
The organomodified trisiloxane surfactant compositions of the present invention were prepared by conventional methods of platinum mediated hydrosilation, as described in Bailey, U.S. Pat. No. 3,299,112, incorporated by reference herein.
Table 1 presents a description of the compositions of the present invention. Some of these compositions are described by the structure:

M*D′M*

where M*=R1Si(CH3)2O0.5;

D′=OSi(CH3)CH2CH(R32)CH2O—(CH2CH2O)r—(CH2CH2O)sR33 where R1, R32, R33, subscripts r, and s are displayed in Table 1.







TABLE 1







Organomodified Trisiloxane Surfactant Compositions















R1
R32
r
s
R33


















Example 1
(CH3)3C—
H
0
11
H



Example 2
(CH3)2CH—
H
0
11
H



Example 3
CH3—
CH3
1
7.5
CH3










Table 2 presents a description of the Comparative Examples A-C trisiloxane and organosilicone polyether based surfactants of the general structure:

MDXD′′YM

where M=(CH3)3SiO0.5; D=OSi(CH3)2; and

D′′=OSi(CH3)CH2CH2CH2O—(CH2CH2O)dR9







TABLE 2







Composition of Comparative Organosilicone Polyether Surfactants









Polyether



Group














X
Y
d
R9
















Comparative
0
1
7.5
CH3



Example A







Comparative
0
1
7.5
H



Example B







Comparative
20
3
7.5
CH3



Example C









Additionally, Comparative Example OPE (Octylphenolethoxylate, containing 10 polyoxyethylene units) is a non-silicone organic surfactant. This product is available as Triton® X-100 from Dow Chemical Company, Midland, Mich.
Table 3 demonstrates the ability of the organomodified trisiloxane composition of the present invention to reduce aqueous surface tension thereby showing utility as surfactants. Surface tension was measured using a Kruss surface tensiometer, with a sand blasted platinum blade as the sensor. Solutions of the various components were prepared at 0.1 wt % in 0.005M NaCl water (Deionized), as an equilibrium aid.
Table 3 displays solutions of these unique compositions provide a significant reduction in surface tension relative to the conventional surfactant.
The compositions of the present invention also provide spreading properties similar to the Comparative Examples trisiloxane surfactants A and B. Additionally, organomodified trisiloxane surfactants of the present invention provide improved spreading relative to the conventional silicone polyether Comparative Example C and conventional organic surfactant Comparative Example OPE.
Spreading was determined by applying a 10 μL droplet, of surfactant solution to polyacetate film (USI, “Crystal Clear Write on Film”) and measuring the spread diameter (mm) after 30 seconds, at a relative humidity between 50 and 70% (at 22 to 25° C.). The solution was applied with an automatic pipette to provide droplets of reproducible volume. Deionized water that was further purified with a Millipore filtration system was used to prepare the surfactant solutions.







TABLE 3







Surface Tension and Spreading Properties










Surface
Spread Diameter (mm)



Tension
Weight % Surfactant













mN/m
0.05%
0.1%
0.2%
0.4%
















Example 1
23.1
 9
11
12
15


Example 2
23.6
10
13
16
25


Example 3
20.7
18
31
48
56


Comparative
20.9
34
53
51
25


Example A


Comparative
20.6
37
53
50
35


Example B


Comparative
23.6
nd
nd
nd
6


Example C


Comparative
31.8
nd
 9
nd
10


Example OPE









Hydrolytic stability was determined for representative compositions of the present invention using HPLC. Solutions of the various compositions were prepared at 0.5 wt % over a pH range from pH 4 to pH 11, and monitored by HPLC for decomposition as a function of time.
Analytical Method
The samples were analyzed by a reverse-phase chromatographic technique using the experimental conditions listed in Table 4.







TABLE 4







Solvent Gradient for HPLC Method












Time (min.)
% Methanol
% Water
% Isopropanol















0.0
70
30
0



15.0
100
0
0



20.0
50
0
50



20.1
70
30
0



25.0
70
30
0









    Detector: ELSD/LTA (Evaporative Light Scattering with Low Temperature Adapter
    Conditions: 30° C., 1.95 SLPM N2 
    Column: Phenomenex LUNA C18 end cap, 5 micron, 75×4.6 mm
    Flow Rate: 1.0 mL/min.
    Inj. Volume: 10 microliters
    Sample: 0.050 g/mL in methanol


Tables 5-8 demonstrate that the compositions of the present invention provide improved resistance to hydrolytic decomposition relative to the standard siloxane based surfactant Comparative Example A, under similar pH conditions.
Comparative Example A shows rapid hydrolysis at pH values below 5 and at pH values above 7, while the organomodified trisiloxane surfactants of the present invention demonstrates a higher resistance to hydrolysis under the same conditions.







TABLE 5







Hydrolytic Stability of Siloxane Based Surfactants by HPLC









Stability: % Siloxane Surfactant Remaining















Time
pH 4
pH 5
pH 7
pH 9
pH 10
pH 11



















Example 1
24
h
100
100
100
100
100
100


Example 1
1
wk
100
100
100
100
100
100


Example 1
2
wk
100
100
100
100
100
100


Example 1
4
wk
100
100
100
100
100
100


Example 1
6
wk
100
100
100
100
100
100


Example 1
9
wk
100
100
100
100
100
100


Example 1
12
wk
100
100
100
100
100
100


Example 1
17
wk
60
100
100
100
100
100


Example 1
23
wk
45
100
100
100
100
100


Example 1
28
wk
30
100
100
100
100
21
















TABLE 6







Hydrolytic Stability of Siloxane Based Surfactants by HPLC









Stability: % Siloxane Surfactant Remaining














I.D.
Time
pH 4
pH 5
pH 7
pH 9
pH 10
pH 11


















Example 2
24
h
100
100
100
100
100
100


Example 2
10
days
100
100
100
100
100
100


Example 2
5
wk
100
100
100
100
100
100
















TABLE 7







Hydrolytic Stability of Siloxane Based Surfactants by HPLC









Stability: % Siloxane Surfactant Remaining















Time
pH 4
pH 5
pH 7
pH 9
pH 10
pH 11



















Example 3
24
h
100
100
100
100
100
100


Example 3
1
wk
40
92
100
99
73
0


Example 3
2
wk
24
82
100
94
48
nd


Example 3
3
wk
16
75
100
92
43
nd


Example 3
5
wk
6
65
100
89
35
nd


Example 3
7
wk
2
55
100
82
29
nd


Example 3
24
wk
0
21
100
50
4
nd


Example 3
31
wk
nd
0.2
100
42
0.3
nd
















TABLE 8







Hydrolytic Stability of Comparative Siloxane Based Surfactants


by HPLC









Stability: % Siloxane Surfactant Remaining















Time
pH 4
pH 5
pH 7
pH 9
pH 10
pH 11



















Comparative
48
h
25
100
100
100
46
nd


Example A


Comparative
1
wk
0
38
100
53
0
nd


Example A









Unlike traditional siloxane based surfactants, which are subject to rapid hydrolysis under acidic and basic conditions (at pH values of 5 or below and at pH values of 9 or above) the organomodified trisiloxane surfactants of the present invention provide increased resistance to hydrolysis relative to traditional trisiloxane alkoxylates (e.g., Comparative Example A). An artifact of hydrolysis is observed as a reduction in spreading properties over time. Therefore solutions of the organomodified trisiloxane surfactants (i.e., Example 3) of the present invention, as well as Comparative Example surfactants (i.e., Comparative Example A) were prepared at desired use levels and pH. Spreading was determined as a function 6f time to illustrate resistance to hydrolysis.
Table 9 displays organomodified trisiloxane surfactants, where Example 3, a superspreader, has improved resistance to hydrolysis, over a pH range from pH 3 to pH 10, relative to a traditional trisiloxane ethoxylate surfactant Comparative Example A. As mentioned above, resistance to hydrolysis was observed by monitoring the spreading properties over time. Here a 0.4 wt % solution was prepared at pH 3, 4, 5 and 10. Spreading determined according to the procedure in Example 4.







TABLE 9







Effect of pH on Spreading Properties Vs Time










Spread Diameter (mm)















Time
Product
pH 3
pH 4
pH 5
pH 10



















0
h
Example 3
43
42
43
38





Comp. Ex. A
34
28
29
27



1
h
Example 3
48
43
46
40





Comp. Ex. A
39
37
27
33



2
h
Example 3
53
44
50
41





Comp. Ex. A
36
30
33
33



4
h
Example 3
47
48
52
39





Comp. Ex. A
41
28
28
29



6
h
Example 3
46
45
48
33





Comp. Ex. A
16
27
27
28



8
h
Example 3
44
42
47
40





Comp. Ex. A
12
31
29
27



24
h
Example 3
21
44
46
28





Comp. Ex. A
12
32
25
25



48
h
Example 3
37
45
43
31





Comp. Ex. A
10
41
25
33



5
days
Example 3
25
41
40
35





Comp. Ex. A
7
30
26
36



1
wks
Example 3
15
37
42
27





Comp. Ex. A
6
17
28
25



2
wks
Example 3
11
19
25
27





Comp. Ex. A
7
7
37
15










The impact of other ingredients on spreading was determined by blending the organosilicone trisiloxane surfactant of the present invention, with a conventional organic based co-surfactant. The co-surfactants are displayed in Table 10.
Blends were prepared as physical mixtures where the weight fraction silicone is represented by α (alpha), indicating that the co-surfactant makes up the balance of the blend ratio. For example when α=0 this indicates that the composition contains 0% of the silicone component and 100% co-surfactant, while an α=1.0 indicates the composition contains 100% silicone, and no (0%) co-surfactant. Mixtures of the two components are represented by the weight fraction α, where α ranges as follows: 0≦α≦1.0. By example when α=0.25 this indicates the surfactant mixture is composed of 25% silicone and 75% co-surfactant. These blends are then diluted in water to the desired concentration for spreading evaluation.
Spreading was determined as described in Example 4, at 0.2 wt % total surfactant.







TABLE 10







Description of Conventional Co-surfactants










ID
Description






IDA-5
Isodecyl alcohol ethoxylate (4-5 EO)



IDA-6
Isodecyl alcohol ethoxylate (5-6 EO)



TMN-6
Trimethylnonylalcohol ethoxylate (6 EO)



Oxo-TDA-5
Oxo-tridecyl alcohol ethoxylate (5 EO)



Oxo-TDA-6
Oxo-tridecyl alcohol ethoxylate (6 EO)



APG
C8-10 Alkylpolyglucoside









Table 11 demonstrates that representative examples of the co-surfactants of the present invention provide favorable spreading results, and in some cases provide an unexpected synergistic enhancement, where the spread diameter of the mixture exceeds that of the individual components.







TABLE 11







Effect of Co-surfactants on Blend Spreading Properties









Wt Fraction (α)



Silicone Surfactant Spread diameter (mm)














Run
Silicone
0
0.25
0.50
0.75
1.0
Co-surfactant

















1
Example 3
47
24
49
52
55
IDA-5


2
Example 3
33
43
51
53
55
IDA-6


3
Example 3
49
48
54
59
55
TMN-6


4
Example 3
47
37
43
47
55
Oxo-TDA-5


5
Example 3
43
34
46
48
55
Oxo-TDA-6


6
Example 3
8
50
58
49
55
APG









The following examples describe the utility and application of these novel surfactant compositions to provide improved flow, leveling and wetting benefits.
A model waterborne modified acrylic lacquer formulation based on Rohm and Haas RHOPLEX® 1421 (pH 9.1), as presented in the Table 12, was prepared. The components were slowly mixed in the order they are listed in Table 12. Two drops of red dye were added to the formulation to allow greater contract of coating photographs. The coatings were applied by standard drawdowns onto opacity charts (manufactured by Leneta Company, Form 2A). The dry film thickness was  ̃1 mil. Visual evaluations were made one hour after application. The samples were rated using the visual aspect measurements on a scale of 0-5, 0 being coatings that are characterized with high occurrence of pin holing and complete lack of flow, leveling and wetting, 5 is characterized as defect free coatings.







TABLE 12







Waterborne Acrylic Coating Formulation










Chemicals
Percentage, %






Surfactant
0.1-1.0



2-(2-Butoxyethoxy)ethanol
10.00



Water
25.00-25.9 



RHOPLEX ® 1421
64.00



Total
100.00 









The flow and leveling and wetting properties of the formulations containing 1% of surfactant Example 10 was compared with 1% of conventional organic wetting agent Comparative Example OPE.
As seen in FIG. 1, formulations containing 1% Comparative Example OPE exhibited a high degree of pinholing and dewetting and a complete lack of flow-leveling and was given a aspect rating of 0.
FIG. 1: Coating made from Table 12 Formulation with 1% surfactant Comparative Example OPE.
In contrast, FIG. 2 shows the improved wetting behavior of formulation with 1% of surfactant Example 3 and was given an aspect ranking of 5.
FIG. 2: Coating made from Table 12 Formulation containing 1% surfactant Example 3.
The surfactants of the present invention are very efficient even at low loadings. Excellent wetting and leveling behavior was observed even at 0.25% loading of surfactant Example 3 with an aspect ranking of 5 (See FIG. 3).
FIG. 3: Coating made from Table 12 Formulation containing 0.25% surfactant Example 3.
A model waterborne polyurethane dispersion (PUD) lacquer formulation based on Daotan® VTW 1236/40WANMP (manufactured by Cytec Surface Specialties Inc.), as shown in the Table 13 was prepared. The components were slowly mixed in the order they are listed in Table 13. Two drops of red dye were added to the formulation to allow greater contract of coating photographs. The coatings were applied by standard drawdown onto 4′′×8′′ cold rolled steel (CRS) panels provided by ACT laboratories. Prior to use, the excess of machine oil was removed from the panels by wiping with delicate task wipes (manufactured by Kimwipes). The dry film thickness was  ̃1 ml. Visual evaluations were made one hour after application. The samples were rated using the visual aspect measurements on a scale of 0-5, 0 being coatings that are characterized with high occurrence of pin holing and complete lack of flow, leveling and wetting, 5 is characterized as defect free coatings.







TABLE 13







PUD lacquer formulation










Chemicals
Percentage, %













Surfactant
1.00



Water
25.00



Daotan ® VTW 1236/40WANMP
74.00



Total
100.00









A 1% formulation containing 1% surfactant was prepared and compared with control formulations containing no wetting agent and containing 1% of conventional organic wetting agent OPE.
FIG. 4 presents a photograph of Daotan® VTW 1236/40WANMP system containing 1% of surfactant Example 3. Instant residual oil emulsification occurs which results in the uniform coating across the entire substrate. No de-wetting was observed and was give an aspect ranking of 5.
FIG. 4: Coating from Table 13 formulation containing 1% surfactant Example 3.
In contrast control formulations with either no wetting agent (See FIG. 5) or 1% of Comparative Example OPE (See FIG. 6) shows complete dewetting and were both given an aspect ranking of 0. Dewetting starts to occur within seconds after perfectly uniform wet layer of lacquer applied to the surface.
FIG. 5: Coating from Table 13 formulation containing 0% surfactant.
FIG. 6: Coating from Table 13 formulation containing 1% surfactant Comparative Example OPE.
A conventional printing ink formulation based on Joncryl 537 system (Johnson Polymer) was prepared to demonstrate the efficacy and advantages of the surfactants of the present invention and is presented in Table 24. Application of the coating was done using automatic film applicator; 25 microns rod at 25 to 30 DIN cup #4 and was allowed to air dry on 3 different substrates: Low-density polyethylene; High-density polyethylene; and Co-extruded polypropylene MB400 (Mobil), with formulations at pH 9.5. Visual evaluations were made one hour after application. The samples were rated using the visual aspect measurements on a scale of 0-5, 0 being coatings that are characterized with high occurrence of pin holing and complete lack of flow, leveling and wetting, 5 is characterized as defect free coatings. The Gloss of the coatings were measured with Byk Gardner glossmeter at 60°.







TABLE 14







Printing Ink Formulation:










Name
Description
Supplier
Parts





Joncryl 537
Acrylic Emulsion
Johnson
60 




Polymer



Dowanol DPnB
Coalascent
Dow
6


Jonwax 35
Wax Dispersion
Johnson
2




Polymer



Pigment paste
Pigment Blue (PB 15:4)
Siegwerk
5



dispersed in Joncryl 678





at 40%




Surfactants:
Flow, leveling and wetting
GE, Dow,
0.5-2


Examples;
agent
Airproducts,



Comparative

Byk Chemie



Examples;





Surfynol 104E





and





Byk 348





Rheolate 210
Thickener
Elementis
1




Specialties



Water
Water
Distilled
To adjust to




Water
100 parts









The efficacy and gloss performance of the surfactants of present invention was compared with appropriate controls and is shown in Table 15. Additionally, a non-ionic Comparative Example Surfynol 104 E which is a non-silicone organic surfactant marketed by Air products and Comparative Example Byk 348 which is a silicone surfactant marketed by Byk Chemie that has the following general structure are also provided.




where Z=—CH2CH2CH2O(CH2CH2O)a(CH2CH(CH3)O)bR2













TABLE 15








Gloss
Gloss






(60
(60
Gloss





Deg)
Deg)
(60 Deg)


Material
Loading
Aspect
LDPE
HDPE
PP







None
0%
0
66
47
78


Comp. Ex. A
1%
4
69
52
67


Comp. Ex. Surfynol
1.50%  
4
67
50
74


104E


Comp. Ex. Byk 348
1%
5
54
50
65


Example 3
0.50%  
5
67
51
76









The formulation presented in Table 14 with surfactant of Example 3 is more efficient than surfactant Comparative Example A, Comparative Example surfynol 104E and Comparative Example Byk 348, provides equal or improved aspect rating even at lower concentrations while maintaining excellent gloss properties on all three substrates.
While the process of the invention has been described with reference to certain embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from the essential scope thereof. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed as the best mode contemplated for carrying out the process of the invention but that the invention will include all embodiments falling within the scope of the appended claims.

## Claims

1. A fluorine-free printing ink composition comprising:
a) at least one silicone composition selected from the group consisting of:
i) a trisiloxane compound of the general formula:


M1D1M2 



wherein,
M1=(R1)(R2)(R3)SiO1/2 
M2=(R4)(R5)(R6)SiO1/2 
D1=(R7)(Z)SiO2/2 

where
R1 is selected from a branched or linear hydrocarbon group consisting of 2 to 4 carbons, aryl, and an alkyl hydrocarbon group of 4 to 9 carbons containing aryl substituents of 6 to 20 carbon atoms; R2, R3 R4, R5, R6 and R7 are each independently selected from the group consisting of 1 to 4 carbon monovalent hydrocarbon radicals, aryl, and a hydrocarbon group of 4 to 9 carbons containing an aryl group; Z is an alkyleneoxide group of the general formula:
R8(C2H4O)a(C3H6O)b(C4H8O)cR9, where R8 is a linear or branched divalent hydrocarbon radical of 2, 3, 5, 6, 7, 8, or 9 carbon atoms; R9 is selected from the group consisting of H, monovalent hydrocarbon radicals of from 1 to 6 carbon atoms and acetyl the subscripts a, b and c are zero or positive and satisfy the following relationships:


2≦a+b+c≦20 with a≧2;


ii) a trisiloxane compound of the general formula:


M3D2M4 



wherein
M3=(R10)(R11)(R12)SiO1/2 
M4=(R13)(R14)(R15)SiO1/2 
D2=(R16)(Z′)SiO2/2 

where R10, R11, R12 R13, R14, R15 and R16 are each independently selected from the group consisting of 1 to 4 carbon monovalent hydrocarbon radicals, aryl, and an alkyl hydrocarbon group of 4 to 9 carbons containing an aryl substituents of 6 to 20 carbon atoms; Z′ is an alkylene oxide group of the general formula:
R17(C2H4O)d(C3H6O)e(C4H8O)fR18, where R17 is selected from a branched or linear divalent hydrocarbon radical of the general formula:


—C4H8O—(C2H4O)—

R18 is selected from the group consisting of H, monovalent hydrocarbon radicals of from 1 to 6 carbon atoms and acetyl the subscripts d, e and f are zero or positive and satisfy the following relationships:


2≦d+e+f≦20 with d≧2; and


iii) a trisiloxane compound of the general formula:


M5D3M6 




wherein

M5=(R19)(R20)(R21)SiO1/2 
M6=(R22)(R23)(R24)SiO1/2 
D3=(R25)(Z′′)SiO2/2 


where
R19, R20, R21, R22, R23, and R24 are each independently selected from the group consisting of 1 to 4 carbon monovalent hydrocarbon radicals, aryl, and an alkyl hydrocarbon group of 4 to 9 carbons containing an aryl substituents of 6 to 20 carbon atoms, R25 is a linear or branched hydrocarbon radical of 2 to 4 carbons; Z′′ is an alkylene oxide group of the general formula:
R26(C2H4O)g(C3H6O)h(C4H8O)iR27, where R26 is a linear or branched divalent hydrocarbon radical of 2, 3, 5, 6, 7, 8, or 9 carbon atoms; R27 is selected from the group consisting of H, monovalent hydrocarbon radicals of from 1 to 6 carbon atoms and acetyl the subscripts g, h and i are zero or positive and satisfy the following relationships:


2<g+h+i≦20 with g≧2; and


b) at least one printing ink resin,

wherein the composition exhibits enhanced resistance to hydrolysis and enhanced wetting, flow and leveling compared to the composition absent said silicone; and,
c) a pigment.

2. The composition of claim 1 wherein R1 and R4 are selected from the group consisting of propyl, iso-propyl, butyl, sec-butyl, iso-butyl and tert-butyl.

3. The composition of claim 1 wherein R2, R3, R5, R6 and R7 are methyl.

4. The composition of claim 1 wherein R8 is a divalent hydrocarbon radical having three carbon atoms.

5. The composition of claim 1 wherein the subscript a ranges from 8 to 12.

6. The composition of claim 1 wherein the subscript b ranges from 0 to 3.

7. The composition of claim 1 wherein the subscript c is 0.

8. The composition of claim 1 wherein R9 is selected from the group consisting of hydrogen and methyl.

9. The composition of claim 5 where the subscript a is 11.

10. The composition of claim 2 where R2, R3, R5, R6 and R7 are methyl.

11. The composition of claim 10 where R8 is a divalent hydrocarbon radical having three carbon atoms.

12. The composition of claim 11 where the subscript a is 11.

13. The composition of claim 12 where the subscripts b and c are both zero.

14. The composition of claim 13 where R9 is hydrogen.

15. The composition of claim 1 where the subscript f is 0.

16. The composition of claim 1 where the subscript e ranges from 0 to 3.

17. The composition of claim 1 where the subscript d ranges from 8 to 11.

18. The composition of claim 1 where R10, R11, R12, R13, R14, R15 and R16 are methyl.

19. The composition of claim 1 where R18 is methyl.

20. The composition of claim 1 where R27 is selected from the group consisting of hydrogen and methyl.

21. The composition of claim 1 where the subscript i is 0.

22. The composition of claim 1 where the subscript h ranges from 0 to 3.

23. The composition of claim 1 where the subscript g ranges from 8 to 11.

24. The composition of claim 1 where R25 is selected from the group of 3 and 4 carbon monovalent hydrocarbon radicals.

25. The composition of claim 1 where R26 is a 3 carbon monovalent hydrocarbon radical.

26. The composition of claim 1 where R19, R20, R21, R22, R23, and R24 are methyl.

27. The composition of claim 1 wherein the printing ink resin is a least one selected from the group consisting of, polyurethanes, acrylics, polyacrylates, epoxies, polyamides, polyesters, alkyds, nitrocellulosics, ketonic resin, maleic resin, polyvinyl chlorides, polyvinyl butyral, polyacrylates, polyvinylics, polyamides, epoxy acrylates, urethane acrylates, styrene acrylics, polyesters acrylates and their relative monomers bearing unsaturations.

28. An aqueous emulsion wherein the discontinuous phase comprises water and the continuous phase comprises the composition of claim 1.

29. An aqueous emulsion wherein the continuous phase comprises water and the discontinuous phase comprises the composition of claim 1.

30. A non-aqueous emulsion wherein the discontinuous phase comprises a non-aqueous hydroxylic solvent and the continuous phase comprises the composition of claim 1.

31. A non-aqueous emulsion wherein the continuous phase comprises a non-aqueous hydroxylic solvent and the discontinuous phase comprises the composition of claim 1.

32. The composition of claim 1 further comprising at least one co-surfactant selected from the group consisting of alkoxylates, ethoxylates, block copolymers of ethylene oxide, copolymers of ethylene oxide, copolymers of propylene oxide, copolymers of butylene oxide, alkyl phenol ethoxylate, alkyl phenol propoxylate, arylarylalkoxylates, amine alkoxylates, amine ethoxylates, fatty acid alkoxylates, fatty alcohol alkoxylates, alkyl sulfonates, alkyl benzene sulfonates, alkyl naphthalene sulfonates, sulfated fatty alcohols, sulfated fatty amines, sulfated fatty acid amides, acid esters of sodium isethionate, esters of sodium sulfosuccinate, sulfated fatty acid esters, sulfonated fatty acid esters, petroleum sulfonates, N-acyl sarcosinates, alkyl polyglycosides, alkyl ethoxylated amines, alkyl acetylenic diols, pyrrilodone based surfactants, 2-ethyl hexyl sulfate, isodecyl alcohol ethoxylates, ethylene diamine alkoxylates, ethylene oxide/propylene oxide copolymers, diphenyl ether Gemini type surfactants, alkyl polyglycosides, and oxo-tridecyl alcohol ethoxylates.

33. The composition of claim 1 wherein the silicone is present in an amount from about 0.01 to about 5 weight percent of the total composition.

34. The composition of claim 1 wherein the silicone is present in an amount from about 0.05 to about 2 weight percent of the total composition.

35. The composition of claim 1 wherein the silicone is present in an amount from about 0.01 to 1 weight percent of the total composition.

36. The composition of claim 1 further including an adhesion promoter.

37. The composition of claim 36 wherein the adhesion promoter is selected from the group consisting of titanium acetyl acetonate, zirconium carbonates, zirconium propionate, zinc oxides, polyaziridines, organofunctional silanes, and polyethylene imine.

38. The composition of claim 1 further including one or more compounds selected from the group consisting of optical brighteners, humectants, UV absorbers, thixotropic reducing agents, sag reducing agents, thickeners, amines, biocides, PE wax dispersion, antifoam agent, wetting agent, coalescing agent, alcohol and water.