MXPA99003850A - Siloxan protective compositions improved for vehicu - Google Patents

Abstract

The brightness and ease of emulsion application The gloss and ease of application of sprayable aqueous organopolysiloxane vinyl protective organopolysiloxane vinyl protective emulsions are both improved by the sprayable aqueous are both improved by the addition of an additive that increases gloss; of an additive that increases shine, the protectors can be formulated to achieve the protectors can be formulated to achieve superior gloss with the same amount of superior gloss with the same amount of active organopolysiloxane or the same brightness or active organopolysiloxane or the same superior gloss with less organopolysiloxane, higher additives or with less polysiloxane organ, preferred gloss increasing additives are those that increase the preferred gloss are organic viscosity builders organic water soluble viscosity enhancers and / or lower amounts of water soluble solids and / or cantid minor ades of particulate solids that increase viscosity, particulates that increase viscosity, inorganic inorg. nic

Description

PROTECTIVE COMPOSITIONS OF SILOXANE IMPROVED FOR VEHICLES TECHNICAL FIELD The present invention pertains to sprayable siloxane-containing protective compositions used to increase gloss and help protect vinyl and other substrates. More particularly, the present invention pertains to protective compositions which are emulsions of aqueous polyorganosiloxanes which may contain less polyorganosiloxane but which result in a comparable or higher gloss compared to commercial formulations.

PREVIOUS TECHNIQUE The protectors for vehicles based on polysiloxane are currently established products in the market. The term "vehicle protectors" means those products that are applied to vinyl, leather, plastics, rubber and other visible surfaces of automobiles, trucks, and other vehicles to increase the gloss of such surfaces and also to protect such surfaces from the damaging effects of sunlight, heat, humidity, etc. Although described as "vehicle protectors", the term "vehicle" is not understood as a restriction in the use of these compositions, which may be equally useful in boats, trains, airplanes, outdoor furniture, etc., and also for a variety of interior uses. Generally protective compositions do not apply to textiles, glass or painted surfaces, the latter of which tend to have a greasy appearance if treated. The term "vehicle" is descriptive of the market where such products were first developed, and which is still the largest market. In use, vehicle guards are applied to a substrate that is to be "protected" such as a car seat, dashboard, armrest, etc., and rubbed with a cloth. The protector can be sprayed directly on the surface to be treated, or it can be sprayed first on a cloth, pad, or the like. As a result of this application, the brightness of the substrate is considerably increased. The evaporation of the aqueous continuous phase leaves an organopolysiloxane coating which can, in some cases, penetrate the polymer substrates, improving the loss of plasticizers from such surfaces due to exposure to the sun and heat. Protectors are often formulated also with UV absorbers, and the net effect is not only the restoration of the "as new" appearance of the vehicle or other product, but also in general the prolongation of the life of the substrates, for example boards. of instruments to which the protector has been applied. While lotion and paste type protectants are available, they have not found acceptance of the sprayable formulations, due not only to their increased difficulty in application to the surface, but also due to their tendency to leave a protective buildup in joints, cracks, and on highly textured surfaces such as vinyl similar to corrugated leather. Examples of such paste and lotion type protectants are provided by U.S. Pat. 5,433,890, which discloses protectants containing both organopolysiloxane functional in amino and polydimethylsiloxane, a polymer that forms a film to increase the abrasion resistance, and morpholine, necessary to activate the polymer that forms a film. These protectors should be left on the surface for a considerable period of time before the excess is cleaned, and maximum efficiency is achieved only with a second coating. The disadvantages of such preparations are readily apparent. In Canadian published application CA 1, 176,828, organopolysiloxane emulsion based polishes of the paste type containing a silicone-soluble UV absorber are described. These polishers have a high proportion of organopolysiloxane, more than about 20 weight percent solids, and an organic thickening agent which provides the pulp-like character and serves to maintain the high level of uniformly dispersed silicone solids. Nevertheless, these compositions are not sprayable, and therefore suffer the disadvantages of other pastes, creams and lotions. On the other hand, they contain a relatively high proportion of organopolysiloxane. The active ingredients of vehicle protectors are organopolysiloxanes. Organopolysiloxanes are relatively expensive, and a typical shield can contain from 20 weight percent to 40 weight percent organopolysiloxane as an aqueous emulsion. Non-aqueous preparations containing organic solvents are not desirable aqueous preparations containing dispersed organic solvents due to the penetrating odors associated with these solvents, but also for environmental reasons. Despite the relatively high amount of organopolysiloxane, studies show that only a relatively small amount, ie 10% to 20% of what is applied, actually ends up on the substrate. It would be desirable to be able to decrease the amount of organopolysiloxane in vehicle protectants without decreasing their performance, or to obtain increased performance at the same level of the active ingredient. Even with the same organopolysiloxane content, improved performance can allow the application rate to be lowered, resulting in greater economy for the buyer.

DESCRIPTION OF THE INVENTION It has now surprisingly been found that the amount of organopolysiloxane in protectants for sprayable aqueous vehicles can be significantly decreased without decreasing performance, when certain additives which increase gloss are included in the formulation. More surprisingly, although they contain less active ingredient, the gloss exhibited by the subject formulations may be equal to or greater than the gloss exhibited by commercial compositions, while maintaining sprayability. Also, compositions containing similar amounts of organopolysiloxane but having increased brightness can be formulated.

BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 illustrates the increase in brightness obtainable through the use of the subject compositions containing 10 weight percent organopolysiloxane solids; Figure 2 illustrates the increase in brightness, * L, obtainable through the use of the subject compositions containing 10 weight percent organopolysiloxane solids; Figure 3 illustrates the increase in color, * C, obtainable through the use of the subject compositions containing 10 weight percent organopolysiloxane solids; Figure 4 illustrates the increase in weight gain of the substrate obtainable through the use of the subject compositions containing 10 weight percent organopolysiloxane solids; Figure 5 illustrates the increase in brightness obtainable through the use of the subject compositions containing 15 weight percent organopolysiloxane solids; Figure 6 illustrates the increase in brightness, * L, obtainable through the use of the subject compositions containing 15 weight percent organopolysiloxane solids; Figure 7 illustrates the increase in color, * C, obtainable through the use of the subject compositions containing 15 weight percent organopolysiloxane solids; Figure 8 illustrates the increase in weight gain of the substrate obtainable through the use of the subject compositions containing 15 weight percent organopolysiloxane solids; Figure 9 illustrates the increase in brightness obtainable through the use of the subject compositions containing 20 weight percent organopolysiloxane solids; Figure 10 illustrates the increase in brightness, * L, obtainable through the use of the subject compositions containing 20 weight percent organopolysiloxane solids; Figure 11 illustrates the increase in color, * C, obtainable through the use of the subject compositions containing 20 weight percent organopolysiloxane solids; and Figure 12 illustrates the increase in weight gain by the substrate obtainable through the use of the subject compositions containing 20 weight percent organopolysiloxane solids.

EXAMPLE Best mode for carrying out the invention The compositions according to the invention are sprayable aqueous organopolysiloxane emulsions. Useful organopolysiloxanes are organopolysiloxane fluids having net viscosities of about 10 cSt to about 1,000,000 cSt, and preferably, about 50 cSt, to about 100,000 cSt. Both organopolysiloxanes, the less and the more viscous, can be useful for particular applications, and mixtures of organopolysiloxanes of both viscosities, low and high, can be particularly effective. The organopolysiloxanes can be poly (dialkyl) siloxanes such as polydimethylsiloxanes, or organopolysiloxanes containing functional groups such as aminoalkyl groups and ethylenically unsaturated groups. In general, such organopolysiloxanes can consist of organopolysiloxanes corresponding to the formula wherein: R is independently a monovalent hydrocarbon radical having from 1 to 18 carbon atoms, a hydroxy radical or a hydrocarbonoxy radical having from 1 to 18 carbon atoms or radicals containing, for example, amino, mercapto, olefinic functional groups or aromatics, a is an average of 0.7 to 2.6 per unit of the organopolysiloxane of the formula (1) and n is from about 10 to 10,000. In this way, both fluids of organopolysiloxanes, branched and linear fluids are suitable. Further examples of organopolysiloxane fluids are those which have repeating units of (-SiR1R2-O-) n (2) wherein R 1 and R 2 are individually Cis or phenyl alkyl groups, preferably methyl groups, and in some cases, aminoalkyl groups such as, but not limited to, C 1 -C 18 alkyl or polyaminopolyalkyl groups such as aminoethylaminopropyl groups, and salts thereof; and unsaturated groups such as vinyl, allyl, propenyl, isopropenyl, and terminal C 4-8 alkenyl. Alkynyl groups, vinyl ether groups, allyl ether groups, and the like may be useful. The organopolysiloxanes can also carry C-? 8 alkoxy groups, preferably methoxy and ethoxy groups. The organopolysiloxanes may terminate with conventional end groups, such as trialkylsilyl, dialkylsilanolyl, dialkylalkoxysyl, alkyldialkoxysilyl, dialkylvinylsilyl, and the like. This list of organopolysiloxane fluids is illustrative and not limiting.

More generally, organopolysiloxanes are those which can be easily dispersed to form aqueous emulsions, and which are stable to gelatinization in the aqueous composition. Preferred are the end-capped polydimethylsiloxanes with dimethylsilanolyl groups, or more preferably, trimethylsilyl groups. Polydimethylsiloxanes that are lightly or moderately branched are also preferred. A further category of preferred organopolysiloxanes are aminoalkyl-functional polydimethylsiloxanes and polyamino-polyalkyl-functional polydimethylsiloxanes having terminal, long, or both (terminal and long) aminoalkyl or polyaminopolyalkyl groups. Mixtures of various organopolysiloxanes can also be used, particularly mixtures of organopolysiloxanes of different viscosities, for example mixtures of low and high viscosity siloxanes, for example, mixtures of siloxanes having viscosities in the ranges of 10 cSt to 10,000 cSt and 1000 cSt. at 1,000,000 cSt, with the siloxane in the last range having a viscosity higher than that in the first interval. The resinous organopolysiloxanes are not suitable for use as the main active ingredient of the protectants, and thus their use is not preferred. However, minor amounts of such organopolysiloxane resins can be added relative to the total organopolysiloxane to improve durability. The organopolysiloxanes are used in the form of an aqueous emulsion, preferably one having a relatively small particle size, for example in the range of 10 nm to 1000 nm, more preferably in the range of 100 nm to 800 nm, and more preferably in the range of 200 nm to 450 nm. The organopolysiloxane emulsions are prepared in the conventional manner, and the organopolysiloxane emulsions both concentrated and diluted are commercially available. For example, Silicone Fluid Emulsions E10, E103P, E1044, E125P, E1656, E677, E60-350, E60-1000 and others are available from Wacker Silicones, Adrian, Michigan, and Wacker-Chemie GmbH, Munich, Germany. . The emulsions of the subject invention may begin with commercial emulsions to which the remaining ingredients are added, or may be prepared by mixing and emulsifying pure organopolysiloxane with the aid of suitable surfactants, and optionally including ingredients such as U.V. protectants, plasticizers, etc. Such emulsions generally contain 40 to 70 weight percent organopolysiloxane, and are diluted with additional water for use. Glycols such as propylene glycol, ethylene glycol, or low molecular weight polyols such as glycerin, etc., may be added during the preparation of the initial emulsion to ensure a stable, easily dispersible emulsion concentrate. Suitable surfactants include such nonionic surfactants as various oxyethylated C-MS alkanols, oxyalkylated alkylphenols, and the like. Anionic and cationic surfactants, for example dioctylsodiosulfosuccinate, alkylsulfonates, etc. Preferred emulsifiers include the various fatty alcohols of average oxyethylated chain length, such as those having from 10 to 18 aliphatic carbon atoms and degrees of oxyethylation from about 3 to about 20. Surfactants suitable for those skilled in the art are well known. Reference may be made to MCCUTCHEONS, Vol. 1: EMULSIFIERS AND DETERGENTS, 1997 North American Edition, McCutcheon's Division, MC Publishing Co., Glen Rock, N.J. The organopolysiloxane emulsions used herein are preferably stable emulsions with small particle size. By the term "stable" with respect to the emulsions it is understood that the emulsions are free of separation for extended periods, generally with a half-life at room temperature of about 2 years or more. The half-life can be evaluated by observing the particle size after storage for one month at 50 ° C. In general, there must be less than a 20% increase in particle size in this period, more preferably less than an increase of 10%. The particle size must be less than 450 nm. Stability can also be evaluated by centrifugation tests. Stable emulsions should exhibit less than 1 inch (2.54 cm) phase separation, more preferably less than 0.5 inch (1.27 cm), and even more preferably less than 0.2 inch (0.508 cm). More preferably, phase separation is not observed. Stable emulsions do not require additional surfactants, thickeners, or other additives in addition to those initially used in the emulsification process to maintain the freedom of separation or coalescence of the dispersed phase. The protectors of the subject invention contain an additive which increases the gloss. It has been surprisingly discovered that additives can be selected which increase the gloss of inorganic thickening agents and water soluble aqueous thickeners, present in exceptionally small amounts such that the protectants remain as sprayable as that term defined herein. Many thickeners have been tested in these categories, and it has been found that they all help to increase shine. Suitable additives that increase the brightness are preferably compositions exhibiting a moderate increase in the viscosity of the aqueous emulsion at low concentration, examples of such water soluble additives are the various copolymers of polyacrylic acid and polyacrylic acid / polyacrylate soluble, for example those available under the brand name Carbopol®; various polyacrylamides: associative polyethers such as polyoxyethylene and polyoxyethylene / polyoxypropylene copolymer polyethers capped with C8-3 o-olefin oxides; various vegetable gums, for example gum tragacanth, acacia gum, gum arabic, carrageenan gum, xanthan gum, and the like, and the various cellulose ethers, for example carboxymethylcellulose, hydroxypropylcellulose, and the like. Among the inorganic thickeners, insoluble in water, the various clay minerals are also suitable, for example bentonite, and fumed silica. In this regard, reference may be made to MCCUTCHEON'S VOLUME 2: FUNCTIONAL MATERIALS, 1997 North American Edition, McCutcheon's Division, MC Publishing Co., Glen Rock, NJ. When poly (carboxylic acid) and similar water-soluble thickeners are used, a maximum brightness increase effect is obtained when such thickeners are at least partially neutralized. For example, polyacrylic acid thickeners such as Carbopol ™ polycarboxylic acids can be neutralized with bases such as alkali metal hydroxides, ammonia, organic amines, and preferably alkanoamines such as mono-, di- and triethanolamine, the latter being particularly preferred. Surprisingly, the moderate thickening capacity of the non-neutralized polyacrylic acid and similar thickeners results in measurable brightness increase. However, the increase in brightness made possible with partially or fully neutralized thickeners is surprising. Suitable neutralization can be obtained, without limitation, in compositions having pH between 6 and 8, preferably between 6 and 7. The water-soluble high-gloss additives of the polyacrylic acid type are used in amounts such that the aqueous viscosity is about 4000 cP or less. The amounts of additives that increase the water-soluble gloss are thus very small, and will vary somewhat with the thickening efficiency. For Carbopol 940, for example, amounts of less than 0.2 weight percent (solids), more particularly less than 0.1 weight percent, are useful. When 0.2 weight percent more of this thickener is used, the compositions are cream-like or paste-like and are not sprayable.

When solid inorganic materials such as clay minerals are used, it is especially important that their concentration be minimized, otherwise a white coating that accumulates in the pores, bends, and other surface irregularities of the treated substrates may be found. In general, the amounts of such thickeners should be less than 2 percent by weight, preferably about 1 percent by weight or less based on the total weight of the protector. Preferred are polyacrylic acid additives neutralized with bases such as alkali metal hydroxide or with organic amines, more preferably with alkanolamines. As indicated, the amount of additive that increases gloss is generally very low, preferably an amount sufficient to increase the viscosity by about 50% and more preferably from 100% to 200% or more, in aqueous dispersions containing from 10-20. % active (organopolysiloxane), and generally sufficient additive to increase the viscosity in the range of 50 cps to 4,000 cps, preferably 50 cP to 2,000 cP, more preferably in the range of 50 cP to 1000 cP, and more preferably in the range from 50 cP to 500 cP. The higher viscosity formulations will not be sprayable. By the term "sprayable" it is meant that the formulations herein can be sprayed or "vaporized" by means of manually operated spray bottles, of conventional trigger pumps. Compositions that can not be vaporized but can leave the container nozzle only as a coherent stream are not considered "sprayable" as this term is used herein. The amount of the additive may be in the range, in percent by weight, from about 0.010 weight percent to about 1.0 weight percent or more, in the case of additives that increase the inorganic brightness, the various vegetable gums, ethers of cellulose, and associative thickeners, and preferably 0.020 weight percent to about 0.2 weight percent, and more preferably from about 0.050 weight percent to about 0.1 weight percent for water soluble polycarboxylic acid thickeners. As can be seen from the very low amounts of additives employed, it is not a goal of the present invention to increase the viscosity of the protector. Rather, the goal is to maintain spray capacity while achieving an increase in brightness and other desirable characteristics such as brightness, color, and weight gain through the substrate. Sprayable formulations require a viscosity of less than about 4,000 cps, a viscosity which can be achieved with Carbopol® polyacrylates in a concentration of only about 0.1 to 0.15 percent by weight. The amount of additive to increase the gloss to achieve a viscosity of 250 cps, for example, is only about 0.075%. It is preferable that the sprayable viscosities be limited to the ranges indicated above. The thickeners should not be confused with non-reinforcing fillers, which are added to products such as silicone gums and other siloxanes in large amounts, generally from 5% to 90% by weight. Such fillers can not be used in the present invention, not only because of their relatively large particle size, but also because as an application to a substrate it could leave significant amounts of solid residue. Plasticizers can be used in small amounts in the subject formulations. Suitable plasticizers include dialkyl phthalates, triaryl phosphates such as tricresyl phosphate, epoxidized soy bean oil, and a variety of liquid polymeric oligomers. Suitable plasticizers are well known. Examples of plasticizers can be found in Volume 2 of MCCUTCHEON'S, previously cited, on pages 235-241. The amount of plasticizer used may be small, preferably less than 10% by weight of the organopolysiloxane actives, more preferably 5% or less, and more preferably 1% or less. Ultraviolet protectants may be included, for example various ultraviolet absorbent dyes, substituted and unsubstituted aminobenzoic acids and their esters, substituted cinnamic acid and its derivatives and esters such as the Wacker Silicones F595 absorbent, and similar compounds well known to those skilled in the art. The technique. Up to about 10% by weight of the composition can comprise ultraviolet absorbers, preferably about 1-8% by weight. Suitable ultraviolet absorbers can be found in volume 2 of MCCUTCHEON'S on pages 316-320.

The formulations may also contain microbicides such as fungicides, bactericides, molds, etc. in effective amounts. Suitable microbicides are, for example, KATHON® CG / ICP and TROYSAN® 395. Other microbicides are well known and commercially available, and a variety is listed in volume 2 of MCCUTCHEON'S on pages 3-9. The formulation may also contain an antifoaming agent. Examples of these can be found in volume 2 of MCCUTCHEON'S on pages 100-125. The wax of all formulations is preferably excluded. Small amounts of wax can be tolerated, particularly soft waxes and those of the microcrystalline type. However, larger amounts of wax increase the susceptibility to bleaching after drying and also the decrease in gloss, particularly in the normal situation where prolonged polishing is not done. More preferably, the wax is substantially excluded from the composition, ie the composition does not contain wax or contains wax in such a small amount that the composition has substantially the same characteristics, particularly after application, that another identical composition does not contain wax . These characteristics can be measured by measuring the viscosity, which must be within 20% of the viscosity without wax, and evaluating the brightness and percentage of increase, which must be substantially the same or less than the characteristics obtained when the wax is absent , or is present in such small amounts that it can be considered that it has been substantially excluded. It is preferable that the protector be free of non-functional organic solvents. Non-functional organic solvents are those common solvents other than relatively low molecular weight, relatively non-volatile glycols and polyols such as ethylene glycol, propylene glycol, diethylene glycol, glycerin and the like, which are added to maintain or help maintain a stable or helpful emulsion. in the process of organosiloxane emulsification. Examples of non-functional solvents include aliphatic and aromatic hydrocarbons, naphtha, Stoddard solvents, kerosene, turpentine, mineral spirits, ligroin, petroleum ether, and the various solvents sold under the NORPAR® and ISOPAR® brands. When such solvents are included, their amounts are preferably less than 2 percent by weight, more preferably less than 1 percent by weight. It is also preferable that the protector be free of film-forming polymer film forming amounts. Examples of such film-forming polymers are water-dispersible and non-soluble polyacrylate polymers generally water-swellable such as those available under the trademark ACRYSOL ™. Such polymers form a film, generally a crosslinked film, after the evaporation of water, particularly in the presence of a crosslinking catalyst or crosslinking monomer. Such polymers can cause an accumulation of polymer film or oxide, either on the substrate, for example at joint locations, grooves, or cracks, or on the spray bottle or applicator. As such film-forming polymers form films by the coalescence of adjacent polymer domains, add an amount of a film-forming polymer in an insufficient amount to form a coherent film, ie, less than 0.1 weight percent solids, not it would deviate from the spirit of invention. To evaluate the effectiveness of the protectors of the present invention, it is necessary to establish a baseline for comparison. Three commercial protectors (C1-C3) are analyzed, which together represent the main portion of the market of sprayable protectors. Some of the physical and chemical characteristics are presented in Table 1 below and the behavioral values are summarized in Table 2. A brief description of the test methods follows. The percentage by weight of solids gives the total percentage of non-volatile components in a protector. The test procedure is to accurately weigh a sample of 2, 000 grams of the protector in an aluminum cup. The cup is then placed in an oven at 105 ° C for two hours. The oven bowl is then removed, cooled to room temperature, and reweighed. The percentage of solids is calculated as: percentage of solids = (final weight / initial weight) x 100% (3) the average particle size of a protective emulsion is determined using a commercial particle size analyzer either from nicomp corporation ( submicron particle gauge model 370) or brookhaven Instruments Corporation (particle gauge model bi-90). The protective emulsions are diluted for evaluation by the manufacturer's instructions with ionized, filtered water. The values given in Table 1 are average particle sizes weighted heavily in nanometers (nm). A centrifugal stability test is used to evaluate the long-term stability of a protective emulsion. An "unstable" emulsion will typically exhibit separation when subjected to high force from a spin. The procedure is to place approximately 50 ml of the protective emulsion to be tested in a 50 ml spin tube (ie from Nalgene Corporation) and firmly place the tube in a fixed angle 45 ° IEC 822A rotor. The sample is then centrifuged for 1 hour at 2000 rpm. When the test is completed, the tube is evaluated for any separation (upper or lower parts). The degree of separation (if present) is given in either inches (in) or millimeters (mm) and indicates whether the separation is at the top or bottom of the centrifuge tube. The specific gravity test gives the density ratio of the protective emulsion to pure water. The test procedure requires that the protective emulsion be equilibrated in a bath at a temperature of 25 ° C. Then the thermally balanced sample is placed in a cup of miget per gallon (Gardner Laboratory) and the weight of the protector is accurately weighed (about 0.1 milligrams). The procedure is repeated using purified water instead of the protector. The specific gravity is determined using: Specific gravity (25 ° C) = (weight of protector) / (weight of water) (4). The pH value gives an indication of the acidity (pH < 7.0) or alkalinity (pH> 7.0) of the protective emulsion. A calibrated pH electrode (Corning model 140 or equivalent) is used in the pure protective emulsion samples. A sufficient amount of time is allowed to ensure that the (digital) pH reading has become constant and that the value is recorded in Table 1. Viscosity values are determined using a Brookfield RVT viscometer with a # 2 rod at 10 rpm. This allows a minimum viscosity of 40 cP (centiPoise) to be measured. Values of less than 40 cP are estimated. The samples are recorded at room temperature (approximately 25 ° C).

TABLE 1 Behavior Test Procedure To evaluate the effectiveness of a protective emulsion, an unbiased test procedure needs to be developed and rigorously followed. In the present it has been chosen to use blue Ford interior vinyl as a primary substrate; however, other types and colors of vinyl have been tested with comparable results. For observations, it has been chosen here to control the change in brightness (85 ° C), brightness (* L), color (* C) and weight gain (milligrams) for treated vinyl sections. The test procedure is as follows. The vinyl is cut into 6"x 6" sections (15.24 x 15.24 cm). Each section is listed and its brightness, * L, * C and weight not treated are measured and recorded. Each brightness reading is an average of 10 independent measurements, and the * L and * C values are an average of 5 independent measurements. Afterwards, each vinyl section is treated with 0.70 ml of the candidate protector applied with precision with a syringe. This amount of protector is selected based on the average use value obtained from studies of preference in a particular consumer (ie the average consumer applies 0.70 ml of the protector for an area of 6"x 6" (15.24 x 15.24 cm)). It is then polished with the protector for 20 seconds using a 4"x 4" (5.08 x 5.08 cm) section of a clean cotton cloth that has been folded in four (ie 1"x 1" (2.54 x 2.54 cm) of cotton pad). Once it is polished, the treated vinyl sections are then placed in an oven at 50 ° C for 1 hour to dry. After drying, each section of vinyl is re-weighed and the brightness measurements are taken, * L and * C (again, averages of 10 independent measurements). For each shield sample, this test procedure is repeated in triplicate. To minimize the effect of random variations on the vinyl sections, all the values in Table 2 are arranged as the difference between the treated and untreated vinyl. The brightness is measured using a Hunter Lab ProGloss 3 brightness meter. Due to the relatively low intrinsic reflectivity, the 85 ° angle fixation is selected to maximize the response (typically 5-20). The color parameters * L and * C are measured using an X-rite 948/968 spectrophotometer, with a computer interface, and equipped with the QA master software. The value * L (brightness) indicates the reflective intensity of the treated vinyl (ie the treated wine appears darker, richer in blue). As this value typically decreases after the treatment, its negative value for easier graphical comparison is presented (ie, - * L). The value * C (color) gives the vividness or lack of brightness of the color of the sample (ie the "blue" of the vinyl). Additional information on these color attributes can be found in X-Rite Corporation's "A Guide to Understanding Color Communication," page 14.

TABLE 2 Protective concentrate example 1 A concentrate concentrate is prepared, formulated to allow further dilution by giving a shield with 10 weight percent of an organopolysiloxane of 350 cSt and 1.5 percent of a UV protector package., as follows. A premix is made consisting of the emulsifiers and oils, which contains 4.75 weight percent of a surfactant ethoxylated with secondary alcohol, 55.0 weight percent of a polydimethylsiloxane of 350 cSt (brand SWS101 350), 8.25 weight percent of a patented "HAL" UV protector package (HAL = hindered amine light stabilizer), and 2.5 weight percent of propylene glycol. The premix is mixed until homogeneous, then 4.75 percent by weight of water is charged and the resulting mixture is subjected to high shear stress to form a water-in-oil emulsion (referred to as "dry glitter"). The remaining water (24.60 percent by weight) is slowly added with continuous high shear to cause the "dry glitter" to reverse and form an oil-in-water emulsion. Once invested, 0.10 percent by weight of a microbicide is added, and 0.05 percent by weight of SE24 (defoamer). The entire emulsion is then mixed under low shear conditions to ensure a uniform product. The resulting emulsion is stable with a particle size of 318 + 5 nm, 67.6 weight percent solids, and no separation in the proofing test.

Protective concentrate example 2 A emulsion concentrate formulated to allow further dilution to give a 10 percent by weight organopolysiloxane shield of 1000 cSt and 1.5 is prepared in the same manner as described in Example 1 of Protectant Concentrate. percent by weight of the UV protector package. The stable emulsion produced in this way has a particle size of 352 + 9 nm, 67.8 weight percent solids, and centrifugation separation of less than 0.0625 inches (1.6 mm).

Example 3 Protective concentrate Prepared in the same manner as described in Example 1 of Protectant Concentrate, an emulsion concentrate formulated to deliver 15 weight percent of an organopolysiloxane of 350 cSt and 1.5 weight percent of the package. of UV protector. The stable emulsion produced in this way has a particle size of 321 + 7 nm, 65.4 weight percent solids, and spin separation of less than 0.0625 inches (1.6 mm).

Example 4 of Protectant Concentrate Prepared in the same manner as described in Example 1 of Protectant Concentrate, an emulsion concentrate formulated to allow additional dilution giving a protector with 15 weight percent of an organopolysiloxane of 1000 cSt and 1.5 percent by weight of the UV protector package. The stable emulsion produced in this way has a particle size of 321 + 7 nm, 65.3 weight percent solids, and centrifugation separation of less than 0.0625 inches (1.6 mm).

Example 5 Protective concentrate Prepared in the same manner as described in Example 1 of Protectant Concentrate, an emulsion concentrate formulated to allow additional dilution giving a protector with 20 weight percent of an organopolysiloxane of 350 cSt and 1.5 percent by weight of the UV protector package. The stable emulsion produced in this way has a particle size of 352 + 9 nm, 65.4 weight percent solids, and centrifugation separation of less than 0.0625 inches (1.6 mm).

Example 6 Protective concentrate Prepared in the same manner as described in Example 1 of Protectant Concentrate, an emulsion concentrate formulated to allow further dilution giving a protector with 20 weight percent of an organopolysiloxane of 1000 cSt and 1.5 percent by weight of the UV protector package. The stable emulsion produced in this way has a particle size of 352 + 9 nm, 65.5 weight percent solids, and there is no separation after centrifugation.

Examples 7-12 of protectors, 10 percent of organopolysiloxane A series of protectants made in accordance with the present invention, containing 10 weight percent of organopolysiloxane, are prepared from the emulsions described in Examples 1 and 2 of Concentrate of Protector previous. The formulations and characterizations detailed in the following tables 3 and 4 are listed. The protectants are made by dissolving CARBOPOL® 940 in the desired amount of deionized water, then adding the emulsion concentrate and mixing until the mixture is evenly dispersed. Triethanolamine is then added to thicken the protector, then 0.10 weight percent of Troysan 395 microbicide is added and the finished protector mixed well. Examples 7 and 8 are comparison examples.

TABLE 3 TABLE 4 Figures 1-4 graphically compare the results shown in Table 4. The results for commercial protectors, C1-C3, are also included in the figures. As clearly indicated in Figures 1-4, the minimally thickened sprayable protectors (examples 9-12) meet or exceed the performance of the commercial protector C1 on all measured attributes, although it contains only 50 percent of the active ingredient of organopolysiloxane. Note that the non-thickened examples, comparison examples 7 and 8, are more deficient in all measured attributes when compared to commercial samples as expected for a protector with fewer active ingredients.

Examples 13-18 of protectants, 15 percent of orqanopolysiloxane A series of protectants made in accordance with the present invention, containing 15 weight percent of organopolysiloxane, are prepared from the emulsions described in Examples 3 and 4 of Concentrate of Protector previous. The formulations and characterizations detailed in the following Tables 5 and 6 are listed. The protectants are made by dissolving CARBOPOL® 940 in the desired amount of deionized water, then adding the emulsion concentrate and mixing until the mixture is evenly dispersed. Triethanolamine is then added to thicken the protector, then 0.10 weight percent of Troysan 395 microbicide is added and the finished protector mixed well. Examples 13 and 14 are comparison examples.

TABLE 5 TABLE 6 Figures 5-8 graphically compare the results presented in Table 6. The results for commercial protectors, C1-C3, are also included in the figures. As clearly indicated in Figures 5-8, the minimally thickened sprayable protectors (examples 15-18) meet or exceed the performance of the market leader, C1, in all measured attributes. Examples of Protectors 15-18 also behave near the level of shield C2, which contains about 30 percent organopolysiloxane (35 weight percent solids) compared to 15 weight percent for the examples of the subject invention . As observed in the 10 percent by weight protectors of the preceding section, a moderately thickened sprayable shield can be made equivalently (or very close) in a 50 percent reduction in active materials.

Examples 19-24 of protectors. 20 percent orqanopolysiloxane A series of protectants made in accordance with the present invention, containing 20 weight percent organopolysiloxane, are prepared from the emulsions described in Examples 5 and 6 of the above Protectant Concentrate. The formulations and characterizations detailed in the following tables 7 and 8 are listed. The protectants are made by dissolving CARBOPOL® 940 in the desired amount of deionized water, then adding the emulsion concentrate and mixing until the mixture is evenly dispersed. Triethanolamine is then added to thicken the protector, then 0.10 weight percent of Troysan 395 microbicide is added and the finished protector mixed well. Examples 19 and 20 are comparison examples.

TABLE 7 TABLE 8 Figures 9-12 graphically compare the results presented in Table 8. The results for commercial protectors, C1-C3, are also included in the figures. As clearly indicated in Figures 9-12, the minimally thickened spray protectors (Examples 21-24) meet or exceed the performance of commercial shields, C1-C3. Surprisingly, the inclusion of a moderate amount of a thickener, 0.075 to 0.100 weight percent, which increases the protectiveness at 100 to 2500 cP, results in a significant increase in protector performance even when the level of polyorganosiloxane is as much as 50%. percent less than the one currently used in the market. The increase in brightness shown in Figure 9 is particularly noticeable in that of Example 24, with 33 percent less active material, exceeding commercial shield, C2, by about 50 percent. By the term "increased gloss" with respect to the compositions of the subject invention is meant that the composition, when applied to vinyl cloth and lightly polished, will exhibit an increase in gloss over the vinyl treated with the same composition minus the additive that increases the brightness. The relative degrees of brightness increase ("contribution") can be controlled by measuring the brightness at 85 ° by conventional techniques. The same test can be applied to other vinyl surfaces, that is to say armrests, dashboards, and similar vinyl. The compositions of the subject invention must include necessary ingredients, ie, water, organopolysiloxane, and additives that increase the gloss, as well as any surfactants necessary to achieve a stable emulsion, ie, one that exhibits no marked separation under storage conditions. expected, or stability similar to the formulations of C1 to C3. However, the compositions of the subject invention may optionally be formulated with only these necessary ingredients, and for the exclusion of other ingredients not mentioned herein. By the term "means of application" is meant a cloth, pad, sponge, towel, or other common means for uniformly applying and / or distributing and / or polishing a protector during application to a substrate. Having now fully described the invention, it will be apparent to one of ordinary skill in the art that many changes and modifications can be made thereto without departing from the spirit or scope of the invention as set forth herein.

Claims (27)

NOVELTY OF THE INVENTION CLAIMS

1. - A sprayable vehicle protector, said protector comprises an aqueous dispersion of an organopolysiloxane active ingredient comprising one or more organopolysiloxane fluids, said one or more fluids individually having a pure viscosity of about 10 cSt to about 1,000,000 cSt, said active ingredient present in an effective amount of less than or equal to 20 weight percent, and an effective amount of an additive that increases brightness, said protector has an emulsion viscosity of less than about 4,000 cP, wherein both , said viscosity of emulsion and the increase in brightness of said protector for vehicles are higher in the presence of said additive that increases the brightness than in the absence of said additive that increases the brightness, said additive that increases brightness is selected from the group that consists of water-soluble thickeners and inorganic thickeners insoluble in water.

2. The protector of claim 1 wherein said active ingredient is present in an amount of about 5 weight percent to about 15 weight percent based on the total weight of the protector.

3. The protector of claim 1 wherein said active ingredient is present in an amount of about 5 weight percent to about 10 weight percent based on the total weight of the protector.

4. The protector of claim 1 wherein said brightness enhancing additive is a water soluble carboxylic acid containing compound which is effective to increase the viscosity of an aqueous organopolysiloxane emulsion.

5. The protector of claim 4 wherein said brightness enhancing additive is selected from the group consisting of neutralized or unneutralized polyacrylic polymers, neutralized or unneutralized polyacrylic / polyacrylate polymers, polyacrylamide polymers, cellulose ethers, vegetable gums, and mixtures thereof.

6. The protector of claim 5 wherein said neutralized or unneutralized polyacrylic or polyacrylic / polyacrylate polymer is present in an amount of less than 0.2 weight percent solids based on the weight of the protector.

7. The protector of claim 1 wherein said brightness enhancing additive is a water insoluble particulate solid which increases the viscosity of the aqueous organopolysiloxane emulsions.

8. The protector of claim 7 wherein said particulate solid is selected from the group consisting of clay minerals.

9. The protector of claim 1 wherein said gloss-enhancing additive comprises both a water-soluble compound capable of increasing the viscosity of an aqueous polyorganosiloxane emulsion and a particulate solid capable of increasing the viscosity of a polyorganosiloxane emulsion. watery 10.

The protector of claim 1 wherein the viscosity of said protector is from about 50 cP to about 2000 cP. 1.

The protector of claim 7 wherein said brightness enhancing additive is present in an amount of about 0.02 weight percent to about 1.0 weight percent based on the total weight of said shield.

12. The protector of claim 1 substantially free of wax.

13. A method for increasing the gloss of a protective emulsion for aqueous, sprayable organopolysiloxane vehicles, said method comprises increasing the viscosity of said emulsion by adding an effective amount that increases the viscosity of an additive that increases the brightness, viscosity of the final protector is less than about 4000 cP.

14. The method of claim 13 wherein said effective amount is from about 0.02 to less than 0.2 percent by weight based on the weight of said protector.

15. The method of claim 13 wherein said additive that increases the brightness causes an increase of more than 50% in the viscosity.

16. The method of claim 13 wherein said sprayable protector has a viscosity of less than 40 cP in the absence of the additive that increases the gloss, and a viscosity of more than 40 cP to about 4,000 cP in the presence of said additive.

17. A process for imparting greater gloss to a substrate, said process comprising: applying to said substrate a protector comprising an emulsion of organopolysiloxane that increases the brightness, aqueous, sprayable containing less than or equal to 20 weight percent of one or more organopolysiloxanes having a pure viscosity of about 10 cSt to about 1,000,000 cSt as a dispersed phase, said emulsion further comprising one or more gloss increasing additives selected from the group consisting of soluble organic polymers that increase viscosity, increasers of inorganic viscosity in amounts of up to about 2 weight percent based on the total weight of said protector, and mixtures thereof.

18. The process of claim 17 wherein said organopolysiloxane is present in an amount of about 5 weight percent to about 15 weight percent.

19. The process of claim 17 wherein said organopolysiloxane is present in an amount of about 5 weight percent to about 10 weight percent.

20. The process of claim 17 wherein said brightness enhancing additive is selected from the group consisting of neutralized or unneutralized polyacrylic polymers, neutralized or unneutralized polyacrylic / polyacrylate polymers, polyacrylamide polymers, cellulose ethers, vegetable gums, and mixtures thereof.

21. The process of claim 20 wherein said gloss increasing additive is selected from copolymers of polyacrylic acid and polyacrylic acid in amounts of less than 0.2 weight percent solids based on the weight of the shield.

22. The process of claim 21 wherein said additive that increases the brightness is at least partially neutralized.

23. The process of claim 22 wherein said additive that increases the partially neutralized gloss is neutralized with an alkanolamine.

24. The process of claim 17 wherein said soluble organic polymer is present in an amount of about 0.02 weight percent to less than 0.2 weight percent based on the total weight of the protector.

25. The process of claim 17 wherein said one or more organopolysiloxanes comprise a first organopolysiloxane having a pure viscosity in the range of 10 cSt to 10,000 cSt and a second organopolysiloxane having a pure viscosity in the range of 1000 cSt. at 1,000,000 cSt, the viscosity of said second organopolysiloxane is higher than that of the first organopolysiloxane.

26. The process of claim 17 wherein said protector is sprayed directly on said substrate.

27. - The process of claim 17 wherein said protector is first sprayed into an application medium and subsequently applied to said substrate.