EP0868211A1 - Surfactant blend of organosilicone and surfactants useful as agricultural adjuvants - Google Patents

Abstract

The present invention provides improved surfactant blends characterized by improved superspreading which comprises from 70 % of organosilicone compounds such as (Me3SiO)2Si(Me) CH2CH2 CH2(OCH2 CH2)7.5OMe mixed with specific water-soluble surfactant(s) characterized by hydrophobic groups having from about 4 to about 12 carbon atoms. This surfactant blend provides clear aqueous solutions characterized by improved spreading efficacy as well as improved surface tension. The surfactant blend is especially useful in agricultural applications as an adjuvant for the delivery of agricultural active ingredients, such as fertilizers, micronutrients, biologicals, pesticides, herbicides, fungicides and growth regulators to treatment sites.

Description

SURFACTANT BLEND OF ORGANOSILICONE AND SURFACTANTS

USEFUL AS AGRICULTURAL ADJUVANTS

BACKGROUND OF THE INVENTION Field of the Invention

The present invention relates to organosilicone/surfactant blends that are characterized by improved claπtv wetting and spreading properties. Prior Art

Nonionic surfactants are commonK used in agriculture as adjuvants to improve ihe efficac> of pesticides, micronutnents. biologicals. herbicides, fungicides, growth regulators and the like Surfactants are important in the application, wetting, spreading and emulsify ing either as pan of the tormulauon or as part of a tank mix

Nonionic surfactants are w ell known lor their ability to reduce the surface tension of aqueous solutions This reduction in surface tension is impoπant for the spreading of solutions on difficult to wet surfaces such as the waxy surface of plant leaves Surtactants aid in uptake Though conventional nonionic surfactants aid in wetting of spra> tormuiauons. they do not proude total wetting on h\ drophobιc leaf surfaces

Organosilicone compounds have been found to be significant!} useful as agricultural adjuvants because of their unique wetting properties These surfactants give surface tension value significanth lower than conventional nonionic surfactants and can provide significant uptake of agricultural chemicals into the plant

The spreading of aqueous solutions due to the organosilicone compounds gives totai wetting as measured by low contact angle on leaf surfaces while conventional surfactants provide for less spreading as indicated by higher contact angles It has been reported that the organosilicone compound must be insoluble in water and dispersed in order to spread extensiveh . i.e.. superspread Organosilicone compounds that were soluble in water did not superspread (Superspreading of Water- Silicone Surfactant on Hydrophobic Surfaces. S Zhu et al.. Colloids Surfaces. a-Phvsicochem. Eng. Aspects 90 ( 1994). 63-78) The interaction between surfactant pairs, while documented, is not consistent. Some pairs demonstrate an ideal behavior where the pair provides the results that would be expected from the mixture whereas some pairs are non-ideal in providing surface tensions lower than that expected. U.S. Pat No. 3.562.786 describes solutions of nonionic organosilicone compounds blended with certain ranges of conventional nonionic and ionic surfactants. The organosilicone compound is claimed to be useful in lowering the aqueous surface tension of organic surfactant solutions The nonionic surfactants used in the patented combinations are primarily non\ lphenol or alcohol ethoxylates However, these materials when used with organosilicone compounds are known to interfere with the spreading characteristics of the organosilicone compounds.

U.S. Pat. No 5.104.647 teaches the synergistic combination of organosilicone compounds with polyalkylene oxide block copolymers which forms dispersions allowing for good surface tension reduction without sacrificing the spreading efficac} of the mixture. Nonvlphenol or alcohol ethoxylates interfere with the spreading characteristics of the organosilicone compounds since they do not form dispersions. While the 5.104.647 patent teaches that the weight fraction of organosilicone compound to po alkylene oxide block copolymer can range from 1 % to 99% and converseh the copolymer from 99% to 1%. the preferred ranges are from 1 % to 50% and 50% to 1 % These later ranges correspond with the ranges taught in the 3.562.786 patent where the weight ratio between the organosilicone compound and the surfactant ranges from 0.001 to 1 to 1/1. In both these instances, the prior art is taught to use less organosilicone compound than surfactant in order to obtain the desired results. No superspreading or lowering of the contact angle was taught Applicants have unexpectedh found that these limitations on the superspreading can be overcome Clear solutions having higher concentrations of organosilicone compound which show lower dynamic surface tension and increased spreading can be obtained over that expected from the two ingredients The surfactant mixture of this invention provides an improved dynamic and equilibrium surface tension values when compared to the individual components of the mixture.

SUMMARY OF THE INVENTION

The present invention provides an improved surfactant blend characterized by improved superspreading which compπses an organosilicone compound as defined herein mixed with specific water-soluble surfactant(s). This surfactant blend provides clear aqueous solutions with low surface tension without sacrificing the spreading efficacy of the mixture The surfactant blend is especiall} useful in agricultural applications as an adjuvant for the delivery of agricultural!} ac e ingredients such as fertilizers, micronutπents. biologicals. and pesticides such as herbicides, fungicides insecticides and growth regulators, to treatment sites

DETAILED DESCRIPTION OF THE DRAWINGS

Figure 1 is a graphic representation of the data of Example 1 illustrating the degree of non-ideal behavior observed with a mixture of BOS and SILWET L-77. Figure 2 is a graphic representation of the data of Example 1 illustrating the synergism in reduction of dynamic surface tension observed with mixtures of SILWET L- 77 and BOS.

Figure 3 is a graphic representation of the data of Example 2 illustrating the synergism in reduction of dynamic surface tension observed with mixtures of SILWET L- 77 and MPOB Na sulfate.

Figure 4 is a graphic representation of the data of Example 2 illustrating the synergism in reduction of dynamic surface tension observed with mixtures of SILWET L- 77 and MBOP Na phosphate

Figure 5 is a graphic representation of the data of Example 3 illustrating the degree of non-ideal behavior observed with mixtures of SILWET L-77 and DA-530. Figure 6 is a graphic representation of the data of Example 4 illustrating the synergism in dynamic surface tension verses bubble surface age for SILWΕT L-77. DSB and their mixtures.

DETAILED DESCRIPTION OF THE INVENTION The organosilicone compound(s) which can be used in the present invention can be represented by the general formula:

MDyD xXi Formula I wherein M represents Me_?SiO, _: (represents Me,SiO or N4e₃Si as necessary to form a chemically complete structure); D represents Me₂SiO: D^" represents MeRSiO: Me equals CHii R equals C_nH_2nO{C₂H₄O)_a(C_?H₆O)_bR^": y ranges from about 0 to 5. preferably zero: x ranges from about 1 to 5. preferably 1 : n ranges from about 2 to 4. preferably 3: a ranges from about 3 to 25. preferably 3 to 15; and b ranges from about 0 to 25. preferably 0 to 15; it being understood that the oxyalkylene groups may be random and/or block mixtures: and R^* can be hydrogen, an alkyl group having 1 to 4 carbon atoms, or an alkyl ester group vvherein the alkyl group of the ester has 1 to 4 carbon atoms. Each R^' can be same or different on any given molecule. Preferably. R^" is hydrogen or a methyl group.

These organosilicone compounds can be represented by the following examples:

(Me₃SiO)₂Si(Me)CH₂CH₂ CH₂(OCH₂ CH₂)₈ OH

(Me₃SiO,₂Si(Me)CH₂CH₂ CH,(OCH₂ CH₂)₈ OAc Me₃SiOSi(Me)₂ OSi(Me)₂ OSi(Me)₂ CH₂CH₂ CH₂(OCH₂ CH₂)₈OH

(Me₃SiO) Si(Me) CH₂CH₂ CH₂(OCH₂ CH₂)_{7 5}OMe

The most preferred organosilicone compound is represented by the following formula:

(Me_?SiO)₂Si(Me) CH₂CH₂ CH₂(OCH₂ CH₂)_{7 5}OMe Formula II also known as SILWΕT L-77. The organosilicone compounds useful in the invention can be prepared by several conventional methods such as by a process that involves forming a mixture of a siioxane polymer containing a silicon-bonded, halogen-substituted monovalent hydrocarbon group and an alkali metal salt of an oxyalkylene polymer and heating the mixture to a temperature sufficiently elevated to cause the siioxane polymer and the salt to react to produce the desired compound. Some of these compounds can be made by hydrosilation of allyl compounds

The water-soluble surtactants or surface acm e agents which provide the useful and unexpected benefits of the compositions of the invention are general!} characterized structural!} as having an elongated non-polar hydrophobic poπion compπsing from about a C₄ to about C_{[ 2} aliphatic moiety and a shoπ polar hydrophilic poπion. These surfactants can be classified as synthetic, si cone-free. shoπ chain, anionic. non-ionic and/or amphoteπc.

If the elongated non-polar poπion of the molecule includes an anion in the aqueous solution, the surfactant is termed anionic. Anionic surfactants include sulfates. phosphates, sulfonates. carboxylates and taurates In the anionic class, the most commercially impoπant anion groups are carbox} (-COOH). sulfonic acid (-SOiH ) and sulfuπc ester (-OSO H)

The anionic surfactants used herein include alkyl and alkyl ether sulfates and sulfonates. alkylary 1 and alkylaryl ether sulfates and sulfonates. alcohol ether sulfates. ether carboxylic acids and salts thereof, α-olefin suifonate salts, alkyl (mono or di) sulfosuccinates. monoalkyl ether sulfosuccmates. alkyl sarcosinates. alkyl monoglyceride sulfate and sulfonates. acyl isethionates. acyl methyl taurates. salts of fatty acid and fatty acid esters, and alkyl. alkylaryl. ethoxylate mono or di phosphate esters salts, fatty alcohol ether phosphate ester salts, condensates of fart}' acids and amino acids, and mixtures thereof. These surfactants can be used in admixture.

As used in this listing, alkyl is intended to mean an aliphatic straight, branched or cyclic C₄-C_!2 carbon chain such as butyl, capnl. caporyl. capryryl. alkylaryl is intended to mean alkyl as defined before and aryl is intended to cover benzene, naphthalene, such as nonylphe I and dibutvlnaphthvl and substituted deπvatn es thereof such as nonvlphenol. diphenyl oxide, alcohol is intended to be coextensive with the definition for alkyl. olefin is intended to cover an unsaturated carbon chain of 4 to 12 carbons, acyl and fatty acid are intended to have a carbon chain of from 4 to 12 carbons, and ether or ethoxylate is intended to cover EO and/or PO of from 1 to 5. preferably from 1 to 4 The surfactant can also have a countenon which can be alkali metal of sodium or potassium, ammonium or mono, di or tn-ethanol amine

These surfactants can be illustrated ammonium or sodium 2-ethylhexyl sulfate or suifonate. sodium octvl sulfate. ammonium nonylphenyl ether sulfate (2 EO) disodium N- octy i sulfosuccinate. dibutyl naphthalene sodium suifonate. sodium mono or di - dodecyl diphem 1 oxide disulfonate. sodium dec} 1 naphthalene suifonate sodium octyl N-methyl taurates. disodium diocty l sulfosuccinate. sodium dec} l lsethionate. sodium nonyl lsethionate. 2-ethylhenanol phosphate mono and di phosphate esters of nonvlphenol ethoxylates (2 EO) sodium butox} ethy 1 acetate and the like Non-ionic surfactants do not dissociate in water but nevertheless are characteπzed a relatively polar poπion and a relativeh non-polar poπion

The nomonic surtactants used herein include fatf} acid glycenne esters, sorbitan acid esters, sucrose fatty acid esters, and polyglyceπne fart} acid esters wherein the fatty acid has from 4 to 10 carbon atoms., higher alcohol ethylene oxide adducts. single long chain polyoxyethylene alk\ 1 ethers, alk} I and alkylary 1 ethoxylates. polyoxyethylene alk} I allyl ethers, polyoxyethylene fatty acid esters, polyoxyethylene glycenne fatty acid esters, polyoxyethylene propylene glycol fatty acid esters, polyoxyethylene sorbitol fatty acid esters, and polyoxyethylene fatty acid amides wherein the fatty acid has from 4 to 10 carbon atoms, polyoxyethylene alky 1 amines, an alkylpyrro done. glucamides. alkylpolyglucosides. mono- and dialkanol amides, a poh oxyethylene alcohol mono- or diamides and alkylamme oxides wherein the aliphatic group ranges from 4 to 10 carbon atoms Amphoteric surfactants form zwitterions in water so that the same molecule can act as either an anionic or a cationic surfactant. The amphoteric surfactants used herein include amino acid, betaine. sultaine. phosphobetaines. imidazoline type amphoteric surfactants.

Amphoteric surfactants useful in the invention can be illustrated by disodium caporylo or capryio or capryrylo beta-aminodipropionate. C₄-C₈ N-alkyI beta- aminopropionic acid and the sodium salt thereof . sodium octyi amphocarboxylate. sodium caporylo or capryio or capryrylo amphoacetate: disodium caporylo or capryio or capryrylo amphodiacetate. sodium capryioampho hydroxypropyl suifonate. sodium capryryl hydroxyproryl suifonate. capry! amidoamine carboxylate. sodium mixed C . amphocarboxylates. and mixtures thereof. By amphocarboxylate is meant to include RC(O NHCH₂CH₂N(R,)CH_:CH₂OH where R represents a fatty alkyl group of 4 to 10 carbons, and R, is an alkylcarboxy group of 2 to 3 carbon atoms in the alkyl group.

Also useful herein are gemini surfactants, which is a term used herein to identify surfactants having two or three hydrophobic groups with a linkage between hydrocarbon chains and two or more hydrophilic groups attached to hydrophobic poπions in the molecule. The hydrophilic and hydrophobic groups can be the same on either side of the linkage or different. A Gemini surfactant can be anionic. non-ionic, or amphoteric.

A particularly preferred group of gemini surfactants includes compounds of the formula:

wherein R independently represents alkyl of from about 4 to about 20 carbon atoms. R, independently represents hydrogen and alkyl of from about 4 to 20 carbon atoms: R-_> independently represents hydrogen. -SO₃M. -OP(O)(OM)₂. -CH₂COOM. CH₂CHOHCH₂SO_?M. wherein M is hydrogen, alkali metal such as sodium, potassium. alkaline earth metal such as magnesium and calcium, ammonium or organic base salt: and R, represents alkylene of from one to about 10 carbon preferably from about 1 to about 4 atoms or -C(O)-R₄-C(O)- wherein R₄ represents alkylene of from 1 to about 10 carbon atoms and aryl. e.g. phenylene. R₃ also represents -0-RτO- wherein R_* represents aliphatic or aromatic moieties of from 1 to about 10 carbon atoms with the proviso that when R-, is alkylene. then R₂ is not hydrogen EO represents ethyleneox}' radicals. PO represents propyleneoxy radicals, a and b are numbers of from 0 to about 100. a is preferabh from about 0 to about 30 and b is preferably from about 0 to 10 When R is hydrogen, b is not zero and when R is other than hydrogen, b is preferably zero Preferabl . R₃ is alkylene and more preferably CH₂ These compounds are more fully disclosed and claimed in the copending application of Tracy et al. owned by the assignee of the present application. S.N.

08/ filed on the same day as the present application, the entire disclosure of which is incorporated herein by reference.

Illustrative examples of water-soluble gemini surfactants useful in the compositions of the present invention include disodium methylene bιs-(octy l phenol sulfate). disodium methylene bιs-<octyl phosphate), disodium methylene bιs-(octyl phenol ethox} ether sulfate). disodium methylene bis-(octyl phenol ethoxy ether phosphate).

As used herein the terms "alkyl^" or "alkylene^" include straight as well as branched chains

It should be noted that mixtures of the desired organic surfactants can also be used in compositions of the present invention in order to achieve desired performance.

Compositions of the invention can also include other surfactants, or additives normal to the industry including active components used as biocides. pesticides and the like with the qualification that the amount of these additional components is insufficient to totally negate the superspreading or other surfactant enhancing characteristics of the compositions of the invention Such auxiliary additives be suitably chosen for a desired composition and generally include inorganic salts such as Glauber salt and common salt, builders, humectants. solubilizing agents. UV absorbers, softeners, chelating agents. and viscosity modifiers.

The organosilicone compound in the blend of organosilicone compound and the desired surfactants of the invention is used in amounts ranging from about 70% to about 95%. preferabh from about 80% to about 95%. and more preferably from about 85% to about 95% by weight based on the actives weight Coπespondingly. the other surfactants of the invention are used in amounts ranging from about 30% to about 5%. preferabh' from about 20% to 5% and more preferabh- from about 15% to about 5% by weight actives

The mixtures of organosilicone and conventional surfactants as disclosed in the invention provide low surface tension and good dynamic surface tension propeπies. allowing coating formulations to rapidh attain low equilibnum surface tensions. The compositions of the invention can be used in treating a surface which rests the spreading of an aqueous treatment solution b} applying to the surface in amount effective to improve the spreading of the treatment solution These mixtures are effective wetting, spreading, leveling and flow control agents for vanous coating applications, especially in water-based systems, paπicularh for water-based coating processes designed for difficult to coat, low surface energy substrates

The surfactant blends of the present invention find paπicular utility as superspreading additives for paints and coatings, adhesives and adhesive controlled release agents, hard surface cleaners and paπicularly as adjuvants for dispersing, wetting and spreading agnculturally active ingredient-containing solutions such as micronutπents. feπi zers. biologicals. and pesticides such as herbicides, fungicides, insecticides, growth regulators, and the like and mixtures thereof

In controlling pests, e.g . weeds using both selective and nonselective herbicides or insects using insecticides, foliage or fruit applications from aqueous solutions have been found to be the most effective means for application Success of foliage sprays depends on a number of factors, paπicularly the nature of the solution and the type of leaf or fruit surfaces involved.

Many plants possess a moisture proof waxy coating (cuticle) on the leaves or fruit which prevents excessive loss of water and is relatively impervious to water nor does water readily penetrate the plant surface.

Plant surfaces are uneven, being ridged or composed of hemispherical cell walls.-' Water droplets assume sphencal shapes with minimum contact surfaces. If the plant pan is in a veπical position or if the spra} droplet has considerable momentum as it strikes the plant, an aqueous spray solution bounce or run off to a large extent.

In many sprays, the bulk of the v olume is made up of water because it lends driving force to the spra} solution Because of the chemical and physical makeup of the plant surface, aqueous sprays are repelled by most plant surfaces: they round up into spherical droplets and tend to run off Even when atomized by high pressure and applied with great force, they do not stick to the wax} surfaces of many plants If they do stick, they stay in place or collect into droplets and present a minimum surface of contact.

The surfactant blends of the present invention can improve the spreading characienstics of the spra} solution, enhance dynamic and equilibnum surface tension values and assist in dispersing the pesticides The present invention is further illustrated in the Example(s) which follow which are intended to illustrate and do not limit the invention. All pans are by weight, all percentages of surfactants/organosilicone compound are by weight based on the actives weight thereof and all temperatures are in degrees C. in the Examples. Specification and appended claims unless set foπh otherwise. EXAMPLE 1 This example demonstrates that a surfactant blend of the compound of Formula II (SILWET L-77) and sodium 2-ethyIhexv l sulfate RHODAPON BOS) displays strong non- ideal solution behavior

The blends for the Examples were prepared by simple admixture The performance of the surfactant mixtures set forth in this invention was evaluated by several methods Surfactant interactions were determined bv equilibnum surface tension measurements by the Wilhelr Plate Method using a russ K-12 Tensiometer at 25°C and dynamic surface tension measurements the Maximum Bubble Pressure Method ( MBPM) using a kruss BP-2 D}namιc Surtace Tensiometer at constant room temperature (22°C)

The degree of interaction tor the surfactant mixtures is expressed as the difference between the expected and the observed \ alues for surface tension Synergy is defined as a reduction m surface tension below that of either individual surfactant Non-ideal mixing is defined as a reduction in surface tension below that expected value for a linear relationship between two surfactant components

The effect of surfactant mixtures on spreading was evaluated by determining the spread ratio of an aqueous solution on a hvdrophobic surface A smooth Parafilm surface was prepared b} a) dipping a clean glass slide into a hot Parafilm solution in cyclohexane. b) evaporating the solvent in an oven at 60°C for one hour, o cooling the slide covered b} Parafilm down to room temperature (22°C) for 30 minutes before using 8 μl (0 008 gram) of a surfactant solution was applied to the smooth Parafilm surface The spread area was recorded at 60 seconds. The spread ratio was calculated by dividing the spread area of 8 μl of distilled water into the spread area obtained using the same volume of surfactant solution

The surfactant solutions were freshh prepared before each evaluation using deionized water

The dynamic surface tension of surfactant mixtures was determined b} the MBPM descnbed earlier in this text Figure 1 illustrates the degree of non-ideal behavior observed with a mixture of BOS and SILWΕT L-77 Although the expected interaction profile for these non-ioruc-anionic mixture is linear, the observed behavior is non-ideal m nature Similar interactions are observed with other amomc surfactants such as sodium octyl sulfate (RHODAPON OLS) and 2-ethylhexanol phosphate (RHODAFAC PEH)

Data on surface tension, contact angle and spreading ratio on the surface of a Parafilm usmg BOS and SILWET L-77 are listed in Table 1 It is seen that addition of 10% to 20% of BOS to SILWΕT L-77 not only improved the claπry of the solution but also improved the spreading propeπies

Table 1

Surface and Spreading Properties of SILWET L-77 RHODAPON BOS Mixtures ipH = 6.7. T = 22°C)

* 0.008 gram of surfactant solution on the Parafilm surface.

** R. spreading factor = spreading area of 0.008 gram of surfactant solution on Parafilm surface after 1 mmute/spreading area of 0 008 gram of DIW on Parafilm surface after 1 minute

Data on dynamic surface tension of SILWET L-77/RHODAPON. BOS and their mixtures are shown in Table 2 Table 2

Dvnamic Surface Tension of SILWET L-77/RHODAPON BOS Mixtures fpH = 6-7, T = 22°C)

Figure 2 shows the svnergism in reduction of dynamic surface tension The mixtures of L-77 BOS showed lower dynamic surface tension values than that of either individual component This indicates that the L-77/BOS complexes diffuse from the aqueous solution to the air/water interface much faster than either L-77 or BOS individual . The faster spreading property of the mixture may be paπially attributed to the svnerεism in the reduction in dvnamic surface tension.

EXAMPLE 2

It has been found that the mixtures of SILWET L-77 and MBOP Na Sulfate [sodium methylene bis-(octyi phenol sulfate)] and the coπesponding phosphate Gemini surfactants demonstrated excellent superspreading propeπies and synergistic interactions in surface tension reduction as well as in dynamic surface tension reduction. The MBOP is a known compound that was disulfated using a sulfur trioxide pyridine complex method and phosphated by standard methods. The data on spreading factor, surface tension, dynamic surface tension, and contact angle on the Parafilm surface are listed in Table 3-5.

Table 3

Surface and Spreading Properties of SILWET L-77 MBOP Sulfate Mixtures

(0.1 %w.t.. pH = 6.7. T = 22⁰O

Table 4

Surface and Spreading Properties of SILWET L-77 MBOP Phosphate Mixtures f0.1 %w.t.. pH = 6.7. T = 22°Q

Table ?

Dynamic Surface Tension of SILWET L-77 MBOP Sulfate and SILWET L77 MBOP Phosnhate Mixtures fθ.lw.t.%. pH = 5.7. T = 22°C)

Plots of dynamic surface tension vs. bubble surface age for L-77 MBOP sulfate and L-77/MBOP phosphate mixtures are shown in Figures 3 and 4. respectively.

From Tables 3 and 4. it is observed that addition of 10% of MBOP sulfate (or phosphate) to SILWΕT L-77 solution not only improved the clarity of the solution, but also improved the superspreading property. Moreover, the mixtures of L-77-MBOP sulfate (or phosphate) produced the same or even lower contact angle on the Parafilm surface and larger spreading area than SILWET L-77 alone. In addition. It is seen that, addition of 10% to 20% of MBOP sulfate (or Phosphate) decreased the surface tension by 0.7 -0.3 dyne/cm compared with 0.1 % of SILWΕT L-77 solution. This is an indication of synergistic interactions between L-77 and MBOP sulfate (or phosphate) surfactants.

From Table 5 and Figures 3 and 4. it is apparent that mixtures of SILWΕT L-

77 MBOP sulfate (or phosphate) showed much lower dynamic surface tension values than that of either individual component above. This indicates that the SILWΕT L-77/MBOP complexes diffuse from the aqueous solution to the air/water interface much faster than either SILWΕT L-77 or MBOP surfactant alone.

EXAMPLE 3

A mixture of SILWΕT L-77 and a non-ionic surfactant branched chain isodecyl alcohol ethoxylate with 4 EO groups (RHODASURF DA-530) also showed good spreading property and non-ideal behavior in surface tension reduction. Figure 5 illustrates the degree of non-ideal behavior observed with mixtures of DA-530 and SILWΕT L-77. Although the expected interaction profile for these non-ionic surfactants is linear, the observed behavior is non-ideal in nature. Data on contact angle and spreading ratio of these mixtures on the Parafilm surface are listed in Table 6. Table 6

Spreading Properties of L-77-RH DASURF DA-530 Mixtures ιO.lw.t.%. T = 22°C)

It is seen that the LP7-DA-530 mixtures containing 10-20% of DA-530 showed basically the same spreading propeπies as SILWΕT L-77 alone

EXAMPLE 4

Mixtures of SILWET L-77 and disodium dodecyl diphenyl oxide, disulfonate (RHODACAL DSB) demonstrated non-ideal behavior in surface tension reduction and synergistic interaction in dynamic surface tension reduction. Data on surface tension and spreading ratio on Parafilm surface are listed in Table 7

Table 7

Surface and Spreadin Properties of L-77 DSB Mixtures

■O.lw.t.%. T = 25°C)

It is seen that mixed solutions of L-77 and DSB had better claπry and showed non- ideal behavior in surface tension reduction. They basically remained the same spreading performance as Silwet L-77. Data on dynamic surface tension are listed in Table 8. Plots of dynamic surface tension vs bubble surface age for SILWΕT L-77. DSB. and their mixtures are shown in Figure 6

Table s

Dynamic Surface Tension of L-77 DSB Mixtures

(0.h> .t.%. T = 22°O

It is clear that dynamic surface tension of the mixed solutions are lower that that of either individual component This indicates the synergistic interaction beuveen these two surfactants

EXAMPLE 5

Mixtures of SILWET L-77 and C8-amphocarboxylate (MIRANOL JEM Cone.) demonstrated non-ideal behavior in surface tension reduction and synergistic interaction

in dynamic surface tension reduction Data on surface tension and spreading ratio on

Parafilm surface are listed in Table 9 Table 9 Surface and Spreading Properties of L-77/.IEM Mixtures ffl.lw.t.%. T 25°Q

It is seen that mixed solutions of L-77 and MIRANOL JEM Cone, showed non- ideal behavior in surface tension reduction and better spreading performance than SILWET L-77 at the same concentration.

EXAMPLE 6

Mixtures of SILWET L-77 (0.09%w.t.), MBOP sulfate (0.005%w.t.). and RHODAPON BOS (0.005%w.t.) demonstrated not only good clarity, but also synergistic interaction in dynamic surface tension reduction and showed much better spreading performance than SILWET L-77 alone. Data on surface tension and spreading ratio on Parafilm surface are listed in Table 10. Data on dynamic surface tension of the mixture are listed in Table 1 1.

Table 10

Surface and Spreading Properties of L-77 MBOP Sulfate/B S Mixtures fθ.lw.t.%. T = 25°C.

It is seen that mixed solutions of SILWΕT L-77. BOS and MBOP sulfate showed non-ideal behavior in surface tension reduction and much better spreading performance that SILWΕT L-77 alone at the same concentration.

Table 11

Dvnamic Surface Tension of L-77 BOS/MBOP Sulfate Mixtures

fQ.l>v.t,%, T = 22⁰C)

From Table 1 1 , it is apparent that mixtures of SILWΕT L-77/MBOP Sulfate/BOS showed much lower dynamic surface tension values than that of either individual component.

Claims

WHAT IS CLAIMED IS:

Claim 1. A surfactant blend providing improved superspreading charactenstics comprising: a) from about 60% to about 95% of an organosilicone compound(s) which can be represented by the general formula:

MDyD 'xM Formula I

wherein M represents Me₃SiO _½; D represents Me₂SiO; D' represents MeRSiO; Me equals CH₃; R equals C_nH_2nO(C₂H₄O)_a (C₃H₆O)_bR' ; and R' can each be the same or different on any given molecule and can be hydrogen, an alkyl group having 1 to 4 carbon atoms, or an alkyl ester group wherein the alky l group of the ester has 1 to 4 carbon atoms, wherein x ranges from about 1 to 5; y ranges from about 0 to 5; n ranges from about 2 to 4; a ranges from about 3 to 25; and b ranges from about 0 to 25; the oxyalkylene groups being random and/or block mixtures of oxyalkylene units; and

b) from about 30% to about 5% of non-silicone containing surfactant(s) wherein the hydrophobic group or groups of the surfactant each independently compnses an aliphatic moiety having from about 4 to about 12 carbon atoms.

Claim 2. A blend as recited in Claim 1 wherein y is zero.

Claim 3. A blend as recited m Claim 2. wherein x is 1.

Claim 4. A blend as recited in Claim 2. wherein a ranges from about 3 to about 15.

Claim 5. A blend as recited in Claim 2. wherein b ranges from 0 to about 15.

Claim 6. A blend as recited in Claim 2. wherein n is 3.

Claim 7. A blend as recited in Claim 1 wherein R' is H or Me.

Claim 8. A blend as recited in Claim 1 wherein the silicone surfactant is selected from the group consisting of :

(Me₃SiO)₂Si(Me)CH₂CH₂ CH₂(OCH₂ CH₂)₈ OH

(Me₃SiO)₂Si(Me)CH₂CH₂ CH₂(OCH₂ CH₂)₈ OAc

Me₃SiOSi(Me)₂ OSi(Me)₂ OSi(Me)₂ CH₂CH₂ CH₂(OCH₂ CH₂)₈OH

(Me₃SiO)₂Si(Me) CH₂CH₂ CH₂(OCH₂ CH₂)_7.5 OMe

Claim 9. A blend as recited in Claim 8 wherein the silicone surfactant is

(Me₃SiO)₂Si(Me) CH₂CH₂ CH₂(OCH₂ CH₂)_7.5OMe

Claim 10. A blend as recited in Claim 1 wherein the surfactant is an anionic surfactant selected from the group consisting of alkyl and alkyl ether sulfates and sulfonates. alkylaryl and alkylaryl ether sulfates and sulfonates. alcohol ether sulfates. ether carboxylic acids and salts thereof, α-olefin suifonate salts, alkyl (mono or di) sulfosuccinates. monoalky! ether sulfosuccinates. alkyl sarcosinates. alkyl monoglyceride sulfate and sulfonates. acyl isethionates. acyl methyl taurates. salts of fatty acid and fatty acid esters, and alkyl. alkylaryl. ethoxylate mono or di phosphate esters salts, fatty alcohol ether phosphate ester salts, condensates of fatty acids and amino acids, and mixtures thereof: wherein alkyl or alcohol represents an aliphatic straight, branched or cyclic C₄-C₁₂ carbon chain; alkylaryl represents alkyl as defined before and aryl covering benzene, naphthalene, and substituted derivatives thereof; olefin represents an unsaturated carbon chain of 4 to about 12 carbons; acyl and fatty acid represent a carbonyl compound having a carbon chain of from 4 to 12 carbons: and ether or ethoxylate represents EO and/or PO of from 1 to 5.

Claim 1 1. A blend as recited in Claim 1 wherein the surfactant is a nonionic surfactant selected from the group consisting of fatty acid glycerine esters, sorbitan fatty acid esters, sucrose fatty acid esters, and polyglycerine fatty acid esters wherein the fatty acid has from 4 to 10 carbon atoms, higher alcohol ethylene oxide adducts. single long chain polyoxyethylene alkyl ethers, alkyl and alkylaryl ethoxylates. polyoxyethylene alkyl ally] ethers, polyoxyethylene fatty acid esters, polyoxyethylene glycerine fatty acid esters, polyoxyethylene propylene glycol fatty acid esters, polyoxyethylene sorbitol fatty acid esters, and polyoxyethylene fatty acid amides wherein the fatty acid has from 4 to 10 carbon atoms, polyoxyethylene alkyl amines, alkylpyrrolidones. glucamides. alkyipolyglucosides. mono- and dialkanol amides, a polyoxyethylene alcohol mono- or diamides and alkylamine oxides wherein the aliphatic group ranges from 4 to 10 carbon atoms.

Claim 12. A blend as recited in Claim 1 wherein the surfactant is an amphoteric surfactant selected from the group consisting of amino acids, betaines, sultaines, phosphobetaines, lmidazoline type amphoteric surfactants and mixtures thereof.

Claim 13. A blend as recited in Claim 1 wherein the surfactant is a surfactant having two or three hydrophobic groups with a linkage beuveen hydrocarbon chains and two or more hydrophilic groups attached to hydrophobic portions in the molecule, wherein the hydrophobes each independently compnse aliphatic moieties having from about 4 to about 12 carbon atoms.

Claim 14. A blend as recited in Claim 1 wherein the hydrophobic group or groups of the surfactant each independent!y compnse an aliphatic moiety having from about 4 to 10 carbon atoms.

Claim 15. A blend as recited in Claim 1 wherein the surfactant is selected from the group consisting of salts of 2-ethylhexyl sulfate. 2-ethylhexanol phosphate, octyl sulfate, dibutyl naphthalene suifonate, isodecyl alcohol ethoxylate (4 EO), dodecyl diphenyl oxide disulfonate. C₈ amphocarboxylate. methylene bis-(octyl phenol sulfate). methylene bis-(octyl phenol phosphate ), methylene bis-(octyl phenol ethoxyether sulfate). and methylene bis-(octyl phenol ethoxyether phosphate).

Claim 16. A blend as recited in Claim 1 wherein said surfactant is of the formula

wherein R independent!y represents alkyl of from about 4 to about 20 carbon atoms. R₁ independently represents hydrogen and alkyl of from 4 to about 20 carbon atoms: R₂ independently represents hydrogen. -SO₃M, -OP(O)(OM)₂, -CH₂COOM, -CH₂CHOHCH2SO₃HM. wherein M represents hydrogen, alkyl or alkaline earth metal, ammonium or an organic base salt: R₃ represents alkylene of from one to about 10 carbon atoms or -C(O)-R₄C(O)- wherein R₄ represents alkylene of from 1 to about 10 carbon atoms or aryl. and -OR₅-O- wherein R₅ represents aliphatic or aromatic moieties of from 1 to about 10 carbon atoms with the proviso that when R₃ is alkylene. then R₂ is not hydrogen, and a and b are numbers ranging from zero to about 100. with the proviso that when R₂ is hydrogen, b is not zero.

Claim 17. A process for treating a hydrophobic surface with an aqueous treatment composition wherein the surface resists spreading of aqueous treatment solutions which compnses forming an aqueous treatment composition with an amount of the composition of Claim 1 effective to improv e spreading of the treatment composition and applying the so made treatment composition to the hydrophobic surface to be treated.

Claim 18. A process as recited in Claim 10 wherein said aqueous treating composition is selected from the group consisting of paints, coatings, adhesives, control release agents, and agricultural adjuvants.

Claim 19. A process for applying an agriculturally active composition to a plant surface which comprises forming an aqueous solution of an agnculturally active composition with the composition of Claim 1 and applying the so made solution to the plant surface.

Claim 20. A process for apph ing pesticides to a plant surface which compnses forming an aqueous solution of pesticide w ith the composition of Claim 1 and applying the so made solution to the plant surface.

Claim 21. A process tor cleaning hard surfaces which comprising contacting the hard surface with a cleaning composition comprising the composition of Claim 1.

Claim 22. A process as recited in Claim 17. wherein y is zero, x is 1, and a ranges from about 3 to about 15.

Claim 23. A process as recited in Claim 19. wherein y is zero, x is 1 , and a ranges from about 3 to about 15.