JPH0587544B2 - - Google Patents

Description

[Detailed description of the invention]

BACKGROUND OF THE INVENTION This invention relates to useful aqueous emulsions of organopolysiloxane resins that are preferred in coating applications over traditional organic solvent systems. The present invention provides both an aqueous silicone emulsion and a method for making the composition. Silicone resins are often selected for applications requiring superior properties. These organopolysiloxane resins are known to exhibit remarkable durability against environmental conditions such as weather and extreme heat and cold. Silicone resins are useful in many applications such as pressure sensitive adhesives and release coatings. Furthermore, they have been found to be particularly useful in the paint industry, which continually seeks coating formulations that exhibit superior properties.
Silicone resin solutions have been used in the paint coating industry as vehicles and binders, an essential part of quality paint formulations. Hitherto, silicone resins have typically been supplied to formulators in the form of solutions, ie, resins containing a high proportion (by weight) of silicone solids in an organic solvent such as xylene or toluene. however,
Recently, the use of such organic solvents has been curtailed due to rising prices of organic materials and increasing environmental concerns. Organic solvent based silicone resins often required expensive and cumbersome contamination control measures and equipment. As described above, recently there has been a trend toward silicone resin systems that are water-based and therefore do not rely on organic solvents. However, these silicone resins, which are particularly useful in the paint and other coatings field, are often immiscible or incompatible with aqueous coating systems. The present invention first provides silicone resins that can be readily dispersed in aqueous emulsion compositions to impart the advantageous properties of silicone resins without the need for significant amounts of organic solvents. As mentioned above, silicone resins are used in high temperature resistant coatings and are generally used as high performance coating vehicles over conventional organic resins in similar applications. Those skilled in the art will appreciate that there are many silicone resins available for coating applications. US Patent No. 4028339
The silicone resins shown in No. 4,056,492 (Merrill) are examples of resins that can be part of the aqueous emulsion compositions of the present invention. The conventionally known silicone resin emulsion is
Although commonly utilized for coating glass fabrics, this composition requires the use of nonionic emulsifiers such as alkyl phenoxy polyethoxyethanol. This system generally requires about 1 part emulsifier for every 7 parts resin solids. When this type of emulsion technique is tried in the resin coating formulations discussed here, as is required by coating formulators, the emulsifier remains in the coating and has a significant negative effect on the coating at high temperatures. Also known are silicone resins based on a combination of nonionic and anionic emulsifiers, which are "acid thickeners based on high molecular weight carboxyvinyl polymers".
(Dumoulin, U.S. Pat. No. 4,052,331, column 6, line 58). Compositions containing small amounts of polyvinyl alcohol of fairly high saponification numbers have also been disclosed. This composition can be formulated, for example, in sunscreens for application to human skin, but acid thickeners are not well tolerated. Use as a coating on unbleached kraft paper is also indicated. On the other hand, the present invention utilizes emulsion systems based on a combination of nonionic and/or anionic emulsifiers and certain neutral vinyl addition polymer compositions. The total amount of emulsifier required for the emulsions of this invention generally ranges from about 0.5 to 50.0 percent based on the weight of silicone resin solids. Furthermore, when a neutral vinyl addition polymer is used as a cooperating reagent, “fissy eye” is formed in the film.
The aqueous composition can be coated more uniformly than the emulsion using a nonionic emulsifier that tends to cause the aqueous composition. Accordingly, a first object of the present invention is to obtain aqueous emulsions of organopolysiloxane resins useful in coating formulations. Another object is to obtain an emulsifier system consisting of a mixture of nonionic and/or anionic and neutral polymeric emulsifiers that is effective for dispersing silicone resins in aqueous coating systems. It is another object to provide a method for making aqueous silicone resin emulsions. These and other objects will be apparent to those skilled in the art upon consideration of the following description and claims. SUMMARY OF THE INVENTION The aqueous silicone emulsion of the present invention comprises (a) about 0 to 50 weight percent monofunctional units of the general formula R ₃ SiO _0.5 , 0 to 60 weight percent difunctional units of the formula R ₂ SiO, about 0 to 60 weight percent difunctional units of the formula RSiO; 0 to 100 weight percent of trifunctional units of _1.5 and 0 to 60 of tetrafunctional units of general formula _SiO2
100 parts by weight of at least one organopolysiloxane resin. In the above formula, R represents a substituted or unsubstituted monovalent hydrocarbon group, usually independently selected from the group consisting of methyl and phenyl. The organopolysiloxane resin has 1.0 to 1.99 R groups per silicon atom. It will be appreciated that in addition to using one type of resin in each emulsion, blends of different organopolysiloxane resins may be used in the present invention. More specific examples of organopolysiloxane resins useful in the emulsions of the present invention include:
About 5-40% by weight _{CH3SiO 1.5} units, 0-35% by weight
( _CH3 ) ₂ SiO units, 15-65% by weight _of ( _C6H5 )
Some are composed of _1.5 units of SiO and 0 to 50% by weight of (C ₆ H ₅ ) ₂ SiO units, with about 1.0 to 1.8 organic groups present per silicon atom. These organopolysiloxane resins are emulsified in water by the method described in the present invention. However, in the field of silicone resins, such resins are typically supplied in solutions consisting of a fixed weight percent of silicone resin solids based on the combined weight of silicone resin solids and solvent. For example, silicone resins are supplied as about 20-90 weight percent solutions in organic solvents such as toluene or xylene. The organic solvent, if present, is not a critical component of the present invention and generally does not reduce the useful properties of these aqueous silicone emulsions in any way. In fact, the presence of a small amount of organic solvent in this emulsion
Other beneficial properties are often imparted to emulsions. Aqueous emulsions of the silicone resins mentioned above are obtained by utilizing mixtures of emulsifiers. The amount of emulsifier required to emulsify 100 parts by weight of resin solids varies widely depending on the process conditions and the selection of ingredients in the emulsion. Those skilled in the art will be able to prepare a variety of aqueous silicone resin emulsions according to the methods presented herein, and will be able to adjust the amount of emulsifier according to the methods presented herein, and further adjust the amount of emulsifier according to individual needs. The amount of emulsifier can be adjusted.
While not limiting the scope of the invention in any way, about 0.25 to 50 parts by weight of the emulsifier mixture are typically required to prepare the aqueous silicone resin emulsions of the invention. It has been discovered by the present invention that certain combinations of emulsifiers are effective in dispersing these silicone resins to provide aqueous emulsions. The emulsifier mixture comprises 5 to 95 weight percent of an emulsifier consisting of a vinyl addition polymer having pendant hydroxyl groups or pendant neutralized carboxyl groups or a mixture of these groups, and a nonionic and/or anionic surfactant or emulsifier. ~5
Consisting of weight percentages. For example, 70 to 75 weight percent vinyl addition polymer emulsifier and 25 to 30 weight percent nonionic and/or anionic surfactant are known to give satisfactory emulsions according to the present invention. Specific examples of each of these types of emulsifiers are provided below. When an effective amount of such an emulsifier mixture is mixed with an organopolysiloxane resin in the presence of water, an aqueous silicone resin emulsion is obtained by use of well known emulsification techniques such as colloid milling. The amount of water is not limited and usually depends on the use of the resulting emulsion. The amount of water is just
It depends on the preselected silicone resin solids content of the resulting emulsion. The method of the present invention involves mixing specific components and then using well-known emulsification techniques.
The above aqueous silicone resin emulsion composition is obtained. DESCRIPTION OF THE INVENTION The silicone resins used in the compositions of the present invention can be prepared by a number of well-known methods, such as by changing the proportion of the organohalosilane component that is hydrolyzed. Typical resins that may be prepared by hydrolysis of a silane mixture include about 60 mole percent methyltrichlorosilane, about 35 mole percent phenyltrichlorosilane, in the presence of water, acetone, and a water-immiscible organic solvent. and about 5 mole percent dimethyldichlorosilane mixture. Generally, the hydrolysis medium can contain about 1.7 to 10 parts of water, 0.2 to 5 parts of acetone, and 0.3 to 5 parts of a water-immiscible organic solvent per part by weight of the silane mixture. The various components of the hydrolysis mixture may be added separately in the desired order. Generally, the organohalosilane is added to a mixture of water, acetone, and an organic solvent. Preferably, when this method is used, 2 to 6 parts of water per total weight of the organohalosilane mixture.
part, about 0.3 to 2 parts of acetone, and about 0.6 to about 2 parts of organic solvent. Adding organohalosilanes to the hydrolysis medium is preferred over the reverse since it reduces the concentration of hydrochloric acid formed during the hydrolysis reaction. Strong hydrochloric acid solutions are not preferred in this example. This is because hydrochloric acid causes acid polymerization of acetone, forming polymerized products that impart an undesirable color to the product and adversely affect the physical properties of the product. A preferred method of preparing the organopolysiloxane resins used in this invention is a dual feed method. This includes organohalosilane mixtures and approx.
0.9 to 5 parts, preferably 0.9 to 1.2 parts of acetone,
Separate containers consist of feeding through separate tubes and then premixing them immediately before hydrolysis. The presence of water causes hydrolysis of organohalosilane, producing acids that polymerize acetone, so if even a small amount of water is present in acetone or in the atmosphere in contact with organohalosilane,
Contact time should be limited. The initial hydrolysis medium, prior to the introduction of the silane blend-acetone mixture, contains about 0 to 4.1 parts of acetone, preferably 0.9 to 4.1 parts of acetone, preferably 0.9 to
Contains 1.2 parts of acetone. The amount of water and organic solvent is
As indicated above, it is preferred to have about 3 to 3.5 parts of water and 0.9 to 1.2 parts of organic solvent per part of the total weight of the organohalosilane blend. The temperature of the hydrolysis mixture can be controlled by the rate of addition of reagents or by heating or, if desired, cooling. Temperatures between about 20°C and about 40°C are preferred during hydrolysis. After all reagents have been added, the mixture is generally agitated for an additional period of time, such as 15 to 30 minutes or more, to effect complete decomposition of the organohalosilane. The mixture is then allowed to stand and the aqueous (low) acid layer is allowed to drain from the organic layer. The organic layer is then freed from the solvent to reach a solids content of up to 100%, depending on each individual's wishes. Organic solvents are removed under reduced pressure or atmospheric pressure. At this point, the desired viscosity is achieved under complete reflux by condensing and crosslinking the silanol units, such as with the aid of catalysts such as iron octoate or celite or mixtures thereof.
Preferably from 15 to 25°C for 20% solids by weight
The resin is thickened, ie, its molecular weight is increased, until it reaches 12 cps. In addition, resin impurities can be caused by e.g. celite.
545 [diatomaceous earth, Johns
Fuller's earth (calcium montmorillonite) and mixtures thereof, or by simply centrifuging. The resulting silanol-containing organopolysiloxane resin has a ratio of organic groups to silicon of about 1.05 to 1. The water-immiscible organic solvents used in the above method for obtaining silicone resins include hydrocarbons such as benzene, toluene and xylene, esters such as butyl acetate and ethyl acetate, and ethers such as diethyl ether. Toluene is the most preferred because it is a good solvent and has a low boiling point. However, in general, any organic solvent that is inert to the hydrolysis reactants during hydrolysis, capable of dissolving and separating the hydrolysis products from the aqueous layer, and immiscible with water may be used. Of course, it is possible to disperse these water-immiscible resins in an aqueous medium by the method presented by the invention. One of the necessary emulsifiers for the aqueous silicone resin emulsion of the present invention is a vinyl addition polymerization product, such as polyvinyl alcohol and/or carboxyvinyl polymer. For example, polyvinyl alcohol is manufactured by Monsanto Plastics and Resins.
The carboxyvinyl polymer is available from BF Goodrich Chemical under the trade name GELVATOL.
Company under the trade name CARBOPOL [CARBOPOL is a water-soluble resin used as a thickener, suspending agent for insoluble components, and emulsion stabilizer to provide a wide range of viscosities and flow properties. Polymer dry powder (100% active), molecular weight 450000-4000000
907, depending on the size of the molecular weight.
910, 941, 934, 940, etc.]. Polyvinyl alcohol is one type of commercially available product. It is produced by hydrolyzing polyvinyl esters, usually acetic esters, with acids or bases. The degree of hydrolysis depends on various conditions. "Fully hydrolyzed" polyvinyl alcohol typically has about 5% residual pendant acetate groups. In the present invention, the degree of residual pendant acetate groups ranges over a fairly wide range, e.g. from about 5 to about 80
%, preferably from about 5 to about 60%, which means that the pendant hydroxyl content varies from about 20 to about 95%, preferably from about 40%.
This means that it varies within a range of ~95%. Carboxy-substituted vinyl addition polymers are also commercially available varieties. This polymer is typically a white powder;
It has a slight acetic acid odor and when dispersed in water becomes viscous when neutralized with, for example, sodium hydroxide or other bases as described below. For the purpose of this invention, three substances, Carbopol 934, 940 and 941
is suitable. When these are neutralized and made into a 0.2% solution, the viscosity changes due to the difference in molecular weight. Operating the Bruckfield test apparatus at 25°C and 20 rpm according to well-known methods,
934 generally ranges from 2050 to 5450 cp, 940 15000
Ranges from ~35000cp, 941 ranges from 1950 to 7000cp. The class of substances known as Carbopol 941 appears to be particularly suitable for the purposes of the present invention. Acidic components are neutralized before use by reaction with bases such as alkali metal or alkaline earth metal hydroxides, carbonates, bicarbonates or amines (primary, secondary, tertiary) or ammonia. Other types of necessary emulsifiers for use in combination with the above polymerized vinyl products include sodium lauryl sulfate, sodium linear alkylbenzene sulfonate, triethanolamine linear alkylbenzene sulfonate, sodium alphaolefin sulfonate, ammonium alkylphenol ethoxylate sulfate. , lauryl ether ammonium sulfate, alkyl ether ammonium sulfate,
Anionic emulsifiers such as dialkyl ester of sodium sulfosuccinate, sodium cumene sulfonate, ammonium xylene sulfonate, ammonium oleate, morpholinium stearate, and dimethylammonium linoleate. Examples of nonionic emulsifiers are well known, such as alkylphenoxypoly(ethyleneoxyethanol), trimethylnonylpolyethylene glycol,
and generally any n-alkyl monoethers that have been commercially available for many years. (See US Pat. No. 4,052,231, supra.) The aqueous silicone resin emulsions of the present invention can be prepared in any of several ways. Generally, the order of addition of the components is not limited. One suitable method involves dispersing the vinyl addition polymer additive in water by stirring and heat until the solids dissolve. The aqueous phase of the emulsion product can be added in two, three or more portions, if desired. Typically, 0.5 to 10 parts by weight of vinyl addition polymer and 0.1 to 50 parts by weight of nonionic and/or anionic emulsifier per 100 parts by weight of silicone resin solids are effective in emulsifying the resin in an aqueous system. It is true. Those skilled in the art can vary the proportions of the components to obtain the desired resin emulsion formulation. Additionally, optional ingredients such as formalin can be added to these emulsions depending on the desired end use without appreciably reducing the properties of the aqueous emulsions. An example of a typical silicone resin used in the emulsions and methods of this invention is SR-141, available from General Electric Company. The composition to be emulsified is then mixed until homogeneous and then emulsified by colloid milling the composition or homogenizing or blending the composition. A useful colloid mill for producing these aqueous resin emulsions on a laboratory scale is the Manton-Gaulin Colloid Mill, 2A.
It is a type. This mill is adjustable from 1 to 40 mils.
With mil spacing, at atmospheric pressure or 5~
Can operate under supply pressure of _40psigN2 . Of course, it is possible for those skilled in the art to scale up the process of the invention to produce these aqueous silicone emulsions on an industrial scale. The viscosity of the resulting emulsion can be adjusted by varying the amount of water included in the blend. This is best accomplished by first forming a premix of the vinyl addition polymer and silicone resin and some water. This premix is
Emulsification can be achieved by mixing a nonionic and/or anionic emulsifier and the remaining water. The following example shows that water may be added in three portions. The organopolysiloxane resin used in the following examples mainly consists of trifunctional units of formula CH ₃ SiO _1.5 (T units) and formula (C ₆ H ₅ )SiO _1.5 (T' units) and trifunctional units of formula (CH ₃ )SiO 1.5 (T' units). ₂ SiO (D units) and (C ₆ H ₅ ) ₂ SiO (D′ units)
It consists of difunctional units of. In the description of each resin, silane (parts by weight) refers to parts by weight of organohalosilane precursor required for the functional units of the resin. Approximate weight and mole percentages of silane are given for the convenience of those skilled in the art. The weight percent siloxane values indicate the approximate number of each type of siloxane unit present in the average resin molecule. The R to Si ratio is an expression used by those skilled in the art to indicate the approximate number of organic groups bonded to one silicon atom, and is a useful measure of the degree of tri- and di-functionality in silicone resins. be.

【table】

TABLE DESCRIPTION OF PREFERRED EMBODIMENTS In order to more clearly describe the invention, the following examples are to be considered illustrative and not limiting of the invention disclosed and claimed herein.
All parts are by weight. Example 1 The silicone resin to be emulsified is the hydrolysis product of a solid resin of increased viscosity consisting of approximately 35.1% methyltrichlorosilane, 15.2% dimethyldichlorosilane and 49.7% phenyltrichlorosilane (by weight). . In a 2 liter stainless steel beaker equipped with an air stirrer, 150 g of solid silicone resin, 50 g of an 85% aqueous solution of nonionic surfactant [50:50 alkylphenoxy poly(ethyleneoxyethanol)-trimethylnonyl polyethylene glycol ether], and water. 300g, mineral spirits 100g, xylene 100g and 10% polyvinyl alcohol aqueous solution (Gelbatol 20/90) 100g. The premix is milled until homogeneous and then colloid milled (4 mil spacing, under atmospheric pressure). The resulting emulsion has a viscosity of 1420 cps, a solids content of 24.7%, and a homogeneous milky white appearance. When a 40 c.c. sample is centrifuged at 3000 RPM for 30 minutes, there is no visible separation at the top or bottom. When this composition is coated on an aluminum panel, a uniform coating is obtained with no creep, although creep is observed when emulsified with only non-ionic components in the blend of this example. Example 2 A blend of 210 g of polytetrafluoroethylene powder (Modern Industrial Plastics Co., Dayton, Ohio, US, Rilube No. 63), 45 g of titanium dioxide pigment, and 45 g of the silicone resin powder described in Example 1 was When prepared in a ball mill for 24 hours, it becomes a homogeneous powder. To this, 100 g of colloidal magnesium silicate 5% aqueous dispersion [RT Vanderbilt, Veegum HV], polyvinyl alcohol.
Add 100 g of a 10% aqueous solution, 20 g of an 85% aqueous solution of an active nonionic emulsifier mixture (Example 1) and 0.5 g of iron octoate catalyst. Ball mill the mixture for 48 hours. The pigmented resin-emulsion composition thus obtained was coated on an aluminum panel, and
Time to cure. A uniform, void-free, good cured film can be obtained. Example 3 187 g of dry and ground silicone resin powder as described in Example 1, 60 g of titanium dioxide, 19 g of nonionic emulsifier (Example 1), 85 g of 10% polyvinyl alcohol solution, 282 g of water, 37 g of perchlorethylene solvent and N- Mix 94g of propoxy-propanol evenly. The aqueous premix of resin is placed in 100 g of a 10% solution of polyvinyl alcohol and 100 g of odorless mineral spirits. Next, 10 g of methylphenyl silicone oil and 1/2 g of iron octoate catalyst are added. The premix is mixed in a stainless steel beaker with an air-drive stirrer until homogeneous. This is then run through a colloid mill set at 4 mil intervals. The resulting paint containing emulsified silicone resin was found to have a solids content of 28.6% and a viscosity of 1034 cps. 40ml sample at 3000rpm for 30
After centrifugation for a minute, no separation is visible to the naked eye at the top or bottom. Coating aluminum panels with paint and curing at 105°C for 1 hour results in a uniform coating without voids. Example 4 2 g of a carboxylated high molecular weight vinyl addition polymer (BF Gudrich, Carbopol 941) are dispersed in 940 g of deionized water at 50° C. with vigorous stirring. Next, 2.8 g of 6-acetoxy-2,4-dimethyl-m-dioxane preservative (Givguard DXN, Givandan, Clifton, New Jersey, USA) and 8.3 g of a 10% aqueous sodium hydroxide solution are added. Next, 81 g of a 10% aqueous sodium hydroxide solution is added. Then add 81 g of 85% active nonionic emulsifier blend and 1757 g of silicone resin solution. The silicone resin has a silicone resin solid content of 80% dissolved in VM&P naphtha solvent, mainly methyltrichlorosilane 8.1%, dimethyldichlorosilane 27.9%, and phenyltrichlorosilane 22.9%.
and diphenyldichlorosilane 41.1% hydrolysis product. (Silicone Resin-B, supra) Disperse the mixture by stirring at high speed. A further 80 g of the nonionic emulsifier mixture (Example 1) and 100 g of water are then added. The premix is mixed and colloid milled at 5 mil intervals under atmospheric pressure. The resulting milky white emulsion has a viscosity of 1573 cps,
The solid content is 51.6% and the PH is 5.8. 40ml
After centrifugation at 3000 rpm for 30 minutes, less than 1 ml of separation was observed at the top or bottom. Example 5 Preservative (Gibendan, Gibguard DXN)
0.5 g of a carboxylated high molecular weight vinyl addition polymer (Carbopol 941), 3 g of a 10% sodium hydroxide aqueous solution, and 366.8 g of water were mixed and dispersed at 60° C. for 1 hour to neutralize the carboxyvinyl polymer. Silicone resin solution 600g active nonionic emulsifier 85%
Mix with 30 g of solution (Example 1). The silicone resin solution is a toluene solution with a resin solid content of 50%, and is mainly produced by hydrolysis of 30 mol% methyltrichlorosilane, 30 mol% phenyltrichlorosilane, 20 mol% diphenyldichlorosilane, and 20 mol% dimethyldichlorosilane. (Silicone Resin-A, supra). Once the resin solution and emulsifier are uniformly mixed, the neutralized carboxyvinyl polymer solution is added. The premix is mixed and then passed through a colloid mill at 5 mil intervals under atmospheric pressure. The resulting silicone resin emulsion has a solids content of 33.1%, a pH of 6.0 and a viscosity of 3000 cps. 40ml sample at 3000rpm
Even after centrifugation for 30 minutes, no separation was observed with the naked eye. Place the emulsion in an air circulating oven for 50 minutes.
It was found that storage stability was good after one month at ℃. Example 6 To 600 g of the silicone resin solution of Example 5 is added 100 g of the polyvinyl alcohol solution (Example 1). Mix the premix and add a solution of 5 g of sodium lauryl sulfate (anionic surfactant) dissolved in 295 g of water. Mix the premix for 1 hour;
It is then colloid milled at 6 mil spacing at atmospheric pressure. The emulsion was found to have a viscosity of 1000 cps, a pH of 7.0, and a solids content of 31.8%. 40ml
Even after centrifuging the sample at 3000 rpm for 30 minutes, no separation was observed with the naked eye at the top or bottom. It was found that a sample of an emulsified silicone resin containing polyvinyl alcohol had good storage stability when kept at 50° C. for one month. Example 7 100 g of the polyvinyl alcohol solution of Example 1 was added to 600 g of the silicone resin solution of Example 5,
Combine the mixture. Next, add 2g of potassium salt (anionic type) of dodecylbenzenesulfonic acid to water.
Add the solution dissolved in 298g. The mixture is mixed for 1 hour and colloid milled at 6 mil spacing at atmospheric pressure. The resulting emulsion has a viscosity of 4100 cps, a PH of 6.3, and a solids content of 31.2%.
Centrifuging a 40 ml sample at 3000 rpm for 30 minutes yields
No separation is seen with the naked eye, only a skin phenomenon on the surface due to dryness. Sample at 50℃
It remained good even after being placed in an oven for one month. Example 8 14.1 g of oleic acid is added to 600 g of the silicone resin solution of Example 5 and the mixture is mixed well.
Next, carboxyl vinyl polymer (Carbopol
941), 0.2 g, 3 g of 28% aqueous ammonium hydroxide solution and 382.7 g of water are added. The premix is stirred for 1 hour and then colloid milled at 6 mil intervals under atmospheric pressure. The resulting emulsion has a viscosity of 2900 cps, a pH of 8.8, and a solids content of 31.9%.
It is. No separation is visible to the naked eye when a 40 ml sample is centrifuged at 3000 rpm for 30 minutes. 50 samples
It was found that the storage stability was good after one month at ℃. Silicone resins of the type used herein are suitable and can be used in the preparation of a variety of paints and coatings. Environmental constraints require companies to either install costly solvent recovery equipment or switch to more environmentally friendly solvent systems. Introducing resin solutions into aqueous systems is useful for policy needs to reduce pollution. Emulsifying current silicone resin compositions in aqueous systems, which has hitherto not been very easy to do, can be easily accomplished with the present invention. The vinyl addition polymers used herein are capable of drying formulated emulsions without the formation of "fish eyes" and creeping that occurs with the use of nonionic surfactant systems. Many modifications may occur to those skilled in the art in light of the above detailed description. Such obvious modifications are included within the scope of the claims herein.

Claims (1)

[Claims] 1 (a) dissolved in up to 500 parts by weight of an organic solvent;
0 to 50 weight percent of monofunctional units of formula R ₃ SiO _0.5 , 0 to 60 weight percent of difunctional units of formula R ₂ SiO, 0 to 100 weight percent of trifunctional units of formula RSiO _1.5 , and 0 to 100 weight percent of trifunctional units of formula RSiO ₂ Tetrafunctional units 0-60
100 parts by weight of at least one organopolysiloxane resin consisting essentially of: (b) 5 to 95 weight percent of an emulsifier selected from polyvinyl alcohol and vinyl polymers having neutralized carboxyl groups in their side chains and mixtures thereof; and a nonionic surfactant. and/or 95 to 5 percent by weight of an anionic surfactant selected from the group consisting of sodium linear alkylbenzene sulfonate and ammonium oleate;
Emulsifier mixture effective for dispersing organopolysiloxane resins in aqueous emulsions from 0.25 to
50.0 parts by weight (the organopolysiloxane resin
(per 100 parts by weight); and (c) an amount of water sufficient to form a stable aqueous emulsion. 2. The aqueous silicone resin emulsion of claim 1, wherein the amount of water is an amount effective to provide an emulsion with a preselected silicone resin content (by weight). 3. The emulsion of claim 2, wherein the amount of water is about 25 to 400 parts by weight per 100 parts by weight of the organopolysiloxane resin. 4. An emulsion according to claim 1, wherein the organic solvent is selected from toluene, xylene and benzene. 5. The emulsion of claim 1, wherein the monovalent hydrocarbon group is selected from the group consisting of methyl and phenyl groups. 6 The organopolysiloxane resin has about 5 to
40 weight percent _{CH3SiO 1.5} units, about 0 to 35 weight percent ( _CH3 ) _2SiO units, about 15 to 65 weight percent ( _C6H5 )SiO _1.5 units, and about 0 to 50 weight percent ( _C6H5 )SiO units.
2. An emulsion as claimed in claim 1, consisting of weight percent ( _C6H5 ) _2SiO units and having from _about 1.0 to 1.8 organic groups per silicon atom. 7. (a) 0 to 50 percent by weight of monofunctional units of the formula R ₃ SiO _0.5 , 0 to 60 difunctional units of the formula R ₂ SiO dissolved in up to 500 parts by weight of an organic solvent;
100 parts by weight of at least one organopolysiloxane resin consisting essentially of 0 to 100 weight percent of trifunctional units of the formula RSiO _1.5 and 0 to 60 weight percent of tetrafunctional units of the formula SiO ₂ ; R is a substituted or unsubstituted monovalent hydrocarbon group, and the organopolysiloxane resin has approximately 1.0 R groups per silicon atom.
(b) 5 to 95 weight percent of an emulsifier selected from polyvinyl alcohol and vinyl polymers having neutralized carboxyl groups in their side chains and mixtures thereof; and a nonionic surfactant and 0.25 to 5% by weight of an anionic surfactant selected from the group consisting of sodium linear alkylbenzenesulfonate and ammonium oleate, effective to disperse said organopolysiloxane resin in an aqueous emulsion; ~50.0 parts by weight (based on 100 parts of said organopolysiloxane resin), and (c) a sufficient amount of water to form a stable aqueous emulsion; and (a), (b) and ( A method for producing an aqueous silicone resin emulsion comprising the step of emulsifying the mixture of c). 8. The method according to claim 7, wherein the emulsification step is performed by a colloid mill. 9. The method of claim 7, further comprising premixing the emulsifier mixture, or a portion thereof, with a portion of the water, and then mixing the emulsifier with the organopolysiloxane resin and the remaining water. . 10. Claim 7, wherein the amount of water is effective to obtain an emulsion having a preselected silicone resin solids content (by weight).
The method described in section. 11. The method of claim 10, wherein the amount of water is about 25 to 400 parts by weight per 100 parts of organopolysiloxane resin. 12. The method of claim 7, wherein the organic solvent is selected from toluene, xylene and benzene. 13. The method of claim 7, wherein the monovalent hydrocarbon groups are independently selected from the group consisting of methyl and phenyl groups. 14 The organopolysiloxane resin has about 5
~40 weight percent _{CH3SiO 1.5} units, about 0-35
Weight percent ( _CH3 ) _2SiO units, about 15-65 weight percent ( _C6H5 )SiO _1.5 units _, and about 0-50
8. The method of claim ₇ , consisting of weight percent ( _C6H5 ) _2SiO units and having about 1.0 to 1.8 organic groups per silicon atom. 15 (a) dispersing one or more emulsifiers selected from polyvinyl alcohol and vinyl polymers having neutralized carboxyl groups in side chains and mixtures thereof; (b) adding an organopolysiloxane resin to the homogeneous mixture; (c) in another water a nonionic surfactant and/or an anionic surfactant selected from the group consisting of sodium linear alkylbenzene sulfonate and ammonium oleate; (d) adding a nonionic and/or anionic surfactant/water mixture to the vinyl polymer/silicone resin premix and mixing until homogeneous; A method for producing an aqueous silicone resin emulsion comprising the steps of emulsifying a siloxane resin to obtain an aqueous silicone resin emulsion.