WAX or SEALANT

if a carnuaba wax has amino-functional silicones in the formula is it a wax or a paint sealant?

Regards
Bud Abraham

AMINO FUNCTIONAL SILICONE POLYMERS

Aminopropyl-terminated siloxanes are used to form a variety of block copolymers including polyamides,polyurethanes and polycarbonates. The generic structure of an aminopropyl terminated silicone fluid is represented above. These silicones are employed to produce silicone modified epoxy resins. They also have improved adhesion to both painted and unpainted metal surfaces allowing use in corrosion resistant coatings and polishes.
Amino functional silicones are reactive additives to both epoxy and urethane formulations.
Aminoalkyl functional T-structure polymers demonstrate the same range of chemical reactivity as the aminopropyl-terminated siloxanes (reactivity with epoxides,isocyanates, carboxylic acids, etc.). The branched polymers are more likely to find application as formulative additive rather than as prepolymers. Typical applications include detergent polishes, leather finishes, and as internal mold releasing agents.


BACKGROUND OF THE INVENTION

Silicone waxes and silicone protectants, particularly those used to polish and or protect automobiles, are liquid or paste compositions that conventionally contain volatile organic solvents such as mineral spirits. Typically, such wax compositions contain about 25-35% volatile organic solvents; indeed, some formulations contain up to about 40% volatile organic solvents. Such volatile organic solvents are not environmentally friendly.

It would be desirable to have silicone wax products and silicone protectants which do not contain volatile organic solvents, yet which are easily applied to both horizontal and vertical surfaces.

SUMMARY OF THE INVENTION

The present invention relates to an aqueous based, gelled silicone compositions, more particularly waxes and protectants, which are substantially free of volatile organic solvents. The silicone gel wax is useful for protecting a variety of painted surfaces, particularly painted metal surfaces such as car exteriors. The silicone gel protectant is useful for protecting and enhancing the appearance of vinyl, leather, rubber and plastic surfaces such as found in car interiors, car trim and car bumpers.

DETAILED DESCRIPTION OF INVENTION

Conventionally, water based system are not compatible with silicone amine functional groups or silicone fluids; when water is mixed with silicone amine functional groups or silicone fluids the resulting composition is cloudy. Surprisingly, the preferred embodiments of the present invention are not cloudy; instead they are transparent.

The Silicone Gel Wax

The silicone gel wax has a viscosity of at least 3000 centipoise, preferably at least about 5000 centipoise, more preferably from about 5,000 to about 120,000 centipoise, most preferably from about 50,000 to about 60,000 centipoise. In the preferred embodiment, the silicone gel wax is clear, that is, transparent. The silicone gel wax is water based; preferably it has less than 10% volatile organic solvents, more preferably less than 5%, most preferably less than about 1%. The silicone gel wax is preferably not an emulsion.

The silicone gel wax comprises: from about 25% to about 80%, preferably about 25% to 50%, more preferably from about 30% to about 38% water;

from about 0.01% to about 15%, preferably from 0.1% to 8%, more preferably from 0.5% to 3 of an amino functional silicone;

from about 0.05% to about 3%, preferably from about 0.1% to about 1%, most preferably from about 0.2% to about 0.5% of a acrylate thickener,

from about 0.01% to about 20%, preferably from about 0.1% to about 15%, more preferably from about 2% to about 12% silicone fluid;

from 0% to about 80%, preferably from about 0.01% to about 80%, more preferably from about 10% to about 70%, even more preferably

from about 25 to about 65%, most preferably from about 45% to about 62%, humectant;

from 0% to about 25%, preferably from 0.01% to about 25%, more preferably from 0.05% to about 8%, most preferably from 0.1% to about 3%, silicone surfactant;

and from 0% to about 10%, preferably from about 0.001% to about 10%, more preferably 0.005% to about 3% fluoropolymer.

Where the acrylate thickener is in acid form, a neutralizer is preferably employed in an amount sufficient to provide the silicone gel wax with a pH of from about 6.5 to about 7. Good results have been obtained employing neutralizer in an amount from about 0.075% to about 0.75%. Preferably the humectant and the water are present in a ratio of from about 1:10 to 10:1, more preferably from about 2.5:1 to 0.5:1, most preferably about a 1.6:1 ratio. Preferably the acrylate thickener and neutralizing agent are present in a one to one ratio. The silicone gel wax is useful to polish a variety of surfaces, particularly painted metal surfaces such as automobile exteriors.

The Silicone Gel Protectant

The silicone gel protectant protects and enhances the appearance of surfaces of materials such as plastics, vinyl, leather, rubber and the like, particularly those materials such as found in car interiors.

The silicone gel protectant comprises: from about 0.01% to about 20%, preferably from about 0.1 to about 15%, more preferably from about 5% to about 12% silicone fluid;

from about 0.01% to about 15%, preferably from about 0.05% to about 10%, more preferably from about 0.1% to about 1%, thickener;

from about 20% to about 80%, from about 25% to about 65%, more preferably from about 30% to about 45% water;

from 0% to about 20%, preferably from 0.01% to about 20%, more preferably from 0.05% to about 10%, most preferably from 0.1% to about 3% silicone surfactant;

from 0% to about 80%, preferably from 0.1% to about 80%, more preferably from 10% to about 70%, even more preferably from 25% to about 65%, most preferably from about 45% to about 62% humectant;

and from 0% to about 10%, preferably from about 0.001% to about 10%, more preferably 0.005% to about 3% fluoropolymer.

The fluoropolymer imparts slip, longevity, and durability to the silicone gel protectant.

In the preferred embodiment, the silicone gel protectant also contains from about 0.01% to about 6%, more preferably from about 0.1% to about 0.3% silicone "beads".

The silicone gel protectant has a viscosity of preferably at least 1000 centipoise, preferably at least 5000, preferably from about 1000 to about 20,000 centipoise, more preferably from about 5000 to about 7000 centipoise, most preferably from about 3500 to about 4500 centipoise.

THE COMPONENTS

The Thickener

The term "thickener" encompasses both the acrylate thickener and the polymeric thickener.

The Acrylate Thickener

An acrylate thickener is employed in the silicone gel wax and preferably the silicone gel protectant. The acrylate thickener is preferably an acrylic-acrylate preferably in acid form and preferably has a equivalent weight of from about 62 to about 110, more preferably from about 72 to about 80, most preferably from about 75 to 77. The weight average molecular weight, in water is preferably greater than about 400,000 preferably greater than about 500,000. The acrylate thickener is preferably water soluble. The acrylate thickener is a suspending and stabilizing agent that is soluble in water and polar solvents. The acrylate thickener swells in water; it is a crosslinked polymer which thickens when neutralized a polyacrylic acid polymer. Suitable acrylate thickeners are, conventionally known as "carbopols" and are commercially available under the tradename such as, Carbamer 940, Carbamer 2623, Carbamer EZ1, Carbamer EZ2, and PEMULAN 1622 from the B.F. Goodrich Company. The preferred acrylate thickener is a polyacrylic acid homopolymer also known as carboxypolymethylene, and is commercially available under the trade name Carbamer 940 from B.F. Goodrich Company. The acrylate thickener imparts a suitable viscosity to the formulation so that it does not run or drip, particularly from the vertical surfaces.

Where the acrylate thickener is in an acid form, a neutralizing agent is preferably employed to provide the aqueous silicone gel wax with a pH preferably from about 6.5 to about 7, to permit the thickener to thicken. Suitable neutralizing agents include conventional bases, such as for example sodium hydroxide, potassium hydroxide and amine containing compound such as triethonolamine, monoethanolamine, lauramine, and cocoamine. The neutralizing agent preferably has from one to sixteen carbon atoms, preferably from 4 to 8 carbon atoms, most preferably 6 carbon atoms. The neutralizing agent has straight chain carbon atoms and at least one amine group. Good results have been obtained employing neutralizer in an amount from about 0.075% to about 0.75%. Preferably the silicone gel wax contains less than 0.3% of the neutralizing agent.

The Polymeric Thickener

For embodiments of the silicon gel protectant in which clarity is not required, polymeric thickeners are suitable. As used herein, the term "polymeric thickener" does not encompass the acrylate thickener. Suitable polymeric thickeners include for example, cellulose gums, acrylic polymers, xanthan gums, and magnesium aluminum silicate are suitable.

The Aminofunctional Silicone

The aminofunctional silicone provides the gloss, durability, and adherence of the silicone gel wax to the underlying surface. The amino-functional silicone preferably has weight average molecular weight from about 800 to about 28,000, more preferably from about 2000 to about 10,000, most preferably from about 4000 to about 5000.

The amino-functional silicone preferably has viscosity of from about 5 to about 1,000 centistokes, more preferably from about 5 to about 100, most preferably from about 10 to about 50 centistokes. The amino-functional silicone preferably has from about 0.1 meq base/g to about 1 meq base/g more preferably from about 0.15 meq base/g to about 0.7 meq base/g, most preferably from about preferably about 0.48 meq/g.

Suitable amino-functional silicones are amine functional silicone siloxane blends, particularly aminoethyl aminopropyl polysiloxane, dimethylpolymers which are methyl silesquioxanes-methoxy terminated, such as Silicone 1706, available from General Electric. Other suitable amino-functional silicones are silicone DC531 available from Dow Corning Company, and Silicone 1708, also available from General Electric Company.

The amino-functional silicones such as Silicone DC 536 from Dow Corning, tend to cloud the composition and are less preferred.

The Silicone Fluid

The silicone fluid is polymeric and is added to increase the viscosity, to enhance rub-out and the durability of the shine in the final appearance of the gel protectant. The silicone fluid is fluid at 20° C., has a weight average molecular weight from about 800 to about 63,000, preferably from about 10,000 to about 30,000, most preferably from about 13,000 to about 28,000, and a viscosity of from about 50 centistokes, to about 10,000 centistokes, preferably from about 300 centistokes to about 1200 v, most preferably 900 to 1,000, centistokes. The silicone fluid is preferably a non-amino silicone fluid. A suitable silicone fluid is a polydimethylsiloxane, having a viscosity of about 1000 centistokes; such a polydimethylsiloxane is available under the trade name "Silicone 200 fluid, 1000 viscosity" from General Electric.

Another suitable, though less preferred silicone fluid, having a molecular weight of about 13,700 and a viscosity of 350, is available as 350 silicone fluid from General Electric.

Optional Ingredients

The Humectant

The humectant, although optional, is highly preferred in both the silicone gel wax and the silicone gel protectant. The humectant is added to the silicone gel wax and to the silicone gel protectant to keep the aminofunctional silicone dispersed, and also to provide clarity to the silicone gel wax. Preferably, the humectant is a straight chain rather than a ring structure and is hygroscopic. Preferably the humectant has 10 or less carbon atoms in the chain. The humectant preferably has from 1 to 5, more preferably from 2 to 3 alcohol groups. Preferably the humectant is a glycol; suitable glycols are, for example, ethylene glycol, and propylene glycol, and glycerin. Glycerin is less preferred.

The Silicone Surfactant
Optionally, though preferably, silicone surfactant is added to both the silicone gel wax and the silicone gel protectant. Silicone surfactants are those organosilane or organosiloxane compounds exhibiting surface active properties. Preferably, the silicone surfactants have a molecular weight of from about 600 to about 10,000, more preferably about 900 to about 6000, most preferably about 3000. Typically, these compounds are composed of condensation products of alkyl-substituted siloxanes, e.g. dimethyl siloxane, copolymerized with condensation products of alkylene oxide, e.g. poly(ethylene oxide). Such compounds are well known in the art. Examples of such compounds are those shown in U.S. Pat. No. 3,299,112, issued to Bailey; U.S. Pat. No. 4,311,695 to Michael S. Starch, issued Jan. 19, 1982; and U.S. Pat. No. 4,782,095, to Mary L. Gum, issued Nov. 1, 1988, the disclosures of which are incorporated herein by reference.

Also, siloxane oligomers described are in U.S. Pat. No. 4,005,028, issued to Heckert et. al. Jan. 25, 1977, the disclosure of which is incorporated herein by reference.

Preferred silicone surfactants for use in the present invention have a weight average molecular weight of from about 500 to 10,000, preferably from about 1,000 to 5,000, most preferably about 3,000, a viscosity at 25° C. of about 20 to 4000 centistokes, preferably 50 to 500 centistokes, more preferably 80 to 200 centistokes and a surface tension at 25° C. in 0.1% concentration in water of 20 to 33, preferably 22 to 30, N/m. Preferred silicone surfactants for use in the present invention are polysiloxane polyethylene glycol copolymers. A suitable polysiloxane polyethylene glycol copolymer silicone surfactant is sold by Wacker Chemical Company of Munich, Germany, under the designation Silicone Fluid L 066.

Another suitable silicone surfactants are oxide modified polydimethylenesiloxanes; suitable silicone surfactants are, for example, polyalkyl alkaline oxide modified polydimethylenesiloxanes. A suitable polyalkylene oxide-modified polydimethylsiloxane block copolymer is available from Osi, under the designation Silwet L 7607, formerly available as Silwet L 7602, CAS No. 68938-54-5, which has a molecular weight of about 3000, an estimated hydrophile-lipophile balance number of about 5 to 8 (as determined by the method of Griffin OFF. Dig.Fed. paint and Varnish Production Clubs, 28, 446 (1956)), a specific gravity of 1.027, flash point of about 260° C., a pour point of about -15° C., an average weight per gallon of 8.54 pounds at 25° C., and an aqueous surface tension of 26.6 Dynes/cm at 0.1% by weight aqueous solution. Another suitable polyalkyl alkaline oxide modified polydimethylenesiloxanes is available under the trade name Silwet 7606 from the OSI Company. Other suitable silicone surfactants are commercially available from Path Silicones, Phoenix Chemical, and General Electric.

The Fluoropolymer

The fluoropolymer, although optional, is preferred. The fluoropolymer imparts slip, longevity, and durability to the silicone gel wax, and to the silicone gel protectant. In the silicone gel protectant, The fluoropolymer preferably has a weight average molecular weight of from about 50,000 to about 200,000, more preferably about 100,000. In the silicone gel protectant, the preferred fluoropolymer is powdered, preferably having a particle size of about 100 microns or less, more preferably less than 1 micron. A suitable fluoropolymer is polytetrafluoroethylene. A suitable polytetrafluoroethylene is available as MP1150 from Dupont. Preferably the fluoropolymer powder is encapsulated in a gel in bead form. Lipo Technologies Inc. prepared polytetrafluoroethylene powder dispersed in silicone 350 and encapsulated in a proprietary gel.

The fluoropolymer employed in the silicone gel wax is preferably an perfluoroalkyl methacrylic copolymer, which is preferably disperseable in water. A suitable perfluoroalkyl methacrylic copolymer is in liquid form and is commercially available as Zonyl 8740 or Zonyl 8607 from DuPont Company.

The Silicone Beads

The silicone beads contribute to the gloss and shine to the silicone gel protectant. Preferably, the silicone beads contain a silicone fluid which is fluid at 20° C., and has a weight average molecular weight from about 800 to about 63,000, preferably from about 10,000 to about 30,000, most preferably from about 13,000 to about 28,000, and a viscosity of from about 50 centistokes, to about 10,000 centistokes, preferably from about 300 centistokes to about 1200 centistokes, most preferably 900 to 1,000, centistokes. The silicone fluid is preferably a non-amino silicone fluid. A suitable silicone fluid has a molecular weight of about 13,700 and a viscosity of 350, is available as 350 silicone fluid from General Electric. A suitable silicone bead, in which the 350 silicone fluid is encased in a gel outer core is commercially available under the designation "nutrient bead" from Lipo Technologies Inc. Such silicone beads have a particle size of 1750 microns, and are dispersed in water.

The Optional Second Aminofunctional Silicone

Preferably, although optionally, a second amino-functional silicone, having a weight average molecular weight from about 5,000 to about 30,000, more preferably from about 10,000 to about 20,000, most preferably from about 12,000 to about 18,000, is added to the silicone gel wax. The amino-functional silicone preferably has viscosity of from about 1 to about 3,000 centistokes, more preferably from about 100 to about 1,000, most preferably from about 200 to about 500 centistokes. The amino-functional silicone preferably has from about 0.04 meq base/g to about 0.5 meq base/g more preferably from about 0.05 meq base/g to about 0.25 meq base/g, most preferably about 0.15 meq/g. Preferably the second aminofunctional silicone volatilizes from the surface to which it is applied and is non-curable.

A preferred second amino-functional silicone is aminoethyl aminopropyl polysiloxane, having a molecular weight of about 15,203, a viscosity of about 200 to about 500 centistokes, and about 0.15 meq base/g. A suitable aminoethyl aminopropyl polysiloxane and is available under the trade name SF 1921 from General Electric. The SF 1921 is a microemulsion having a continuous phase of silicone in water, and a discontinuous phase of silicone 350. These micro-emulsions may also contain some volatile organic solvents typically less than 1.0% and thus may provide some trace amount of volatile organic solvents to the final formulation of the aqueous silicone gel wax composition; accordingly they are less preferred. The amino-functional silicone is dispersed in the silicone gel wax and does not separate upon standing.

Additional Optional Ingredients

Additional optional ingredients may be added as desired, for example, fungicides, colorants, preservatives, bactericides ultraviolet light absorbers and perfume. A suitable preservative is polymethoxybicyclic oxazolidine, available under the trade name Nuosept C from Costec Inc. Optional ingredients are typically added from 0 to about 20%, preferably from about 0.5% to 20%, more preferably from about 5% to about 10%.

Preferably the silicone gel wax contains less than 0.01% of a salt, particularly sodium chloride. Preferably the gel contains less than 0.5% gum, such as cellulose gum, which provide a sticky formulation that is quite difficult to remove.

As used herein, the phrase "molecular weight" when used in reference to a polymer, refers to weight average molecular weight unless indicated otherwise.

As used herein the term "substantially free of volatile organic solvent" means that there is less than about 5% volatile organic solvents. Volatile organic solvents may be present as a component of the silicones, depending upon the source of the silicones.

Application of the Silicone Gel Wax

The silicone gel wax is evenly applied to the substrate surface such as with a soft cloth and allowed to dry. In the preferred embodiment, when the silicone gel wax dries and forms a light haze, the silicone gel wax is then rubbed out to provide a glossy finish.

Application of the Silicone Gel Protectant

The silicone gel protectant is evenly applied to the substrate surface such as with a soft cotton cloth and allowed to dry. Then the silicone gel protectant was wiped off with a cotton cloth.

All percentages are by weight unless otherwise stated.

EXAMPLE 1

An silicone gel wax having the following formulation was prepared:
______________________________________
INGREDIENT AMOUNT
______________________________________
Water 35.3%
Propylene Glycol 57%
Carbon Carbamer 940 (Acrylic-
0.3%
acrylate thickener in acid
form)
Triethanolamine 0.3%
GE Silicone, 1706 (amino
1%
functional silicone)
Silwet 7607 silicone surfactant
1%
350 Silicone Fluid 4%
1000 Silicone Fluid 0.5%
Preservative Nuosept C
0.4%
Perfumes, dye 0.2%
______________________________________


The silicone gel wax composition was prepared by first hydrating the carbon Carbamer 940 in the water in a lightening mixer with side sweep blades. The Carbamer and water were mixed thoroughly for about 4 to 5 hours, then the mixture was allowed to settle typically at least 2 to 3 hours. The remaining ingredients were added one after the other, typically within about 5 minutes of each other. Next the propylene glycol was added followed by the triethanolamine. The amino functional silicone, the GE 1706 was added. The 350 and 1000 silicone fluid were added. Finally the preservatives and fragrance were added. The ingredients were mixed slowly so as not to entrap air.

EXAMPLE 2

A silicone gel wax was prepared having the following formulation:
______________________________________
INGREDIENT AMOUNT
______________________________________
Water 36.3%
Carbon Carbamer 940 (Acrylic-
0.3%
acrylate thickener in acid
form)
Propylene Glycol 50%
Silwet 7606 silicone surfactant
0.5%
Zonyl 8740 perfluoroalkyl
0.01%
methacrylic copolymer
GE Silicone, 1706 (amino
1%
functional silicone)
SGSF 1921 optional amino
1%
functional silicone (aminoethyl
aminopropyl polysiloxane)
Triethanolamine 0.3%
1000 Silicone fluid 10%
Preservative Nuosept C
0.4%
Perfumes, dye 0.2%
______________________________________


The silicone gel wax was prepared as in Example 1, except that the 350 Silicone was not added and the SGSF 1921 aminofunctional silicone was added.

EXAMPLE 3

A silicone gel protectant having the following formulation was prepared:
______________________________________
INGREDIENT AMOUNT
______________________________________
Water 38.3%
Carbon Carbamer 940 (Acrylic-
0.2%
acrylate thickener in acid
form)
Propylene Glycol 50%
triethanolamine 0.2%
Silwet 7606 silicone surfactant
0.5%
1000 Silicone fluid 10%
Preservative Nuosept C
0.4%
PTFE beads 0.1%
Silicone beads 0.1%
Perfumes, dye 0.2%
______________________________________
PTFE- polytetrafluoroethylene


The silicone gel protectant was prepared by first hydrating the Carbon Carbomer 940 in the water in a lightening mixer with side sweep blades. Next the propylene glycol was added followed by the triethanolamine. The silicone fluid 1000 was added. Next, the preservatives were added. The Teflon.RTM. bead and the silicone beads were added, then the fragrance and dye were added.

Evaluation of Silicone Gel Wax

The silicone gel wax from Examples 1-2 was applied by hand using a soft cloth or sponge to various portions the painted surface of an exterior of an new, red, automobile. The silicone gel wax was allowed to dry, then buffed with a clean cloth. For comparison, conventional liquid waxes were applied to other surfaces.

After the silicone gel wax was applied, an initial gloss measurement were determined as 90-95% gloss from the surface at a 60° angle using a BYK gloss meter from the BYK Company, according to the manufacturer's instructions.

Water was applied to the car; the water formed discrete, tight beads on the areas to which the silicone car wax had been applied.

After the initial gloss reading was taken, the car was subjected to multiple washes in a commercial "brushless" car wash which employed warm water, about 110° C. water and floppy rubber belts rather than brushes to clean the car. Intermittent gloss readings were taken as indicated in Table 1.
TABLE 1
______________________________________
Gloss measurements for Silicone Gel Wax
______________________________________
Gloss Gloss Gloss Gloss
Initial after 5 after 10
after 15
after 20
Gloss washes washes washes
washes
______________________________________
Trunk 92.7 90 88.9 89.6 89.6
with Gel
Wax
______________________________________
Initial 5×
10×
15×
20×
______________________________________
Hood 91.6 89.4 89.4 87.6 87
with Gel
Wax
Roof 89.6 89.5 89.9 88.8 87.8
with Gel
Wax
______________________________________


The gloss readings in Table 1 indicate that after 20 washes there is virtually no change, less than 5% in the gloss values as compared to the initial gloss. areas which received the silicone gel wax comparison with areas had a higher gloss than areas which had received conventional liquid.

Aqueous silicone gel wax from Examples 1-2 was also applied by hand using a soft cloth or sponge to 15 (3"×6") coated steel panels having painted surface of automotive paint. The silicone gel wax was allowed to dry, then buffed with a clean cloth. For comparison, conventional wax products were applied to control panels. The panels were subjected to about 1008 hours of accelerated weathering. The results are shown below in table 2.

The metal panels were exposed to QUV accelerated weathering re-exposure using UVA-340 lamps in cycles of 8 hours UV light at 60° C., and 4 hours condensation at 50° C., for 1008 hours. Gloss was measured at 60° and 20°.
______________________________________
60° Gloss
20° Gloss
Surface
Specimen No.
O P Δ
O P Δ
Tension
______________________________________
0 Weeks
Initial
Readings
Comparative
Products
A1 88 10
2 95 10
3 93 10
B1 95 10
2 93 10
3 95 10
C1 94 10
2 93 10
3 94 10
D1 94 10
2 91 10
3 94 10
silicone gel
wax
E1 94 10
2 96 10
3 95 10
Week 1
Comparative
Products
A1 93 93 0 83 83 0 10
2 95 94 1 92 86 6 10
3 95 95 0 89 89 0 10
B1 94 93 1 89 88 1 10
2 95 94 1 92 86 6 10
3 95 94 1 83 83 0 10
C1 96 92 4 90 88 2 10
2 95 94 1 87 85 2 10
3 94 92 2 87 82 5 10
D1 94 94 0 90 87 3 10
2 95 93 2 87 83 4 10
3 94 92 2 86 84 2 10
silicone gel
wax
E1 91 90 1 75 74 1 10
2 95 95 0 93 84 9 10
3 95 95 0 91 85 6 10
Week 2
Comparative
Products
A1 93 91 2 83 82 1 9
2 95 93 2 92 84 8 9
3 95 93 2 89 83 6 9
B1 94 91 3 89 83 6 9
2 95 92 3 92 86 6 9
3 95 92 3 92 86 6 9
C1 96 91 5 90 75 15 9
2 95 92 3 87 84 3 9
3 94 90 4 87 75 12 9
D1 94 93 1 90 86 4 9
2 95 92 3 87 79 8 9
3 94 91 3 86 86 0 9
silicone gel
wax
E1 91 87 4 75 72 3 9
2 95 92 3 83 82 11 9
3 95 83 2 91 86 5 9
Week 3
Comparative
Products
A1 93 93 0 83 87 -4 9
2 95 94 1 92 85 7 9
3 95 95 0 89 84 5 9
B1 94 91 3 89 86 3 9
2 95 94 1 92 89 3 9
3 95 93 2 83 82 1 9
C1 96 94 2 90 85 5 9
2 95 94 1 87 84 3 9
3 94 92 2 87 74 13 9
D1 94 95 -1 90 87 3 9
2 95 923 3 87 88 1 9
3 94 93 1 86 85 1 9
silicone gel
wax
E1 91 91 0 75 70 5 9
2 95 95 0 93 81 12 9
3 95 94 1 91 84 7 9
Week 4
Comparative
Products
A1 93 92 1 83 83 0 7
2 95 93 2 92 84 8 7
3 95 94 1 89 84 5 7
B1 94 92 2 89 89 82 7
2 95 93 2 92 82 10 7
3 95 92 3 83 78 5 7
C1 96 91 5 90 81 9 7
2 95 93 2 87 83 4 7
3 94 81 3 87 73 14 7
D1 94 93 1 90 82 8 7
2 95 90 5 87 80 7; 7
3 94 90 4 86 84 2 7
silicone gel
wax
E1 91 87 4 75 65 9 7
2 95 92 3 93 82 11 7
3 95 93 2 91 85 6 7
Week 5
Comparative
Products
A1 93 92 1 83 80 3 5
2 95 93 2 92 79 13 5
3 95 93 2 89 82 7 5
B1 94 92 2 89 79 10 5
2 95 92 3 92 80 12 5
3 95 92 3 83 78 5 5
C1 98 90 6 90 79 11 5
2 95 90 5 87 74 13 5
3 94 89 5 87 68 19 5
D1 94 92 2 90 82 8 5
2 95 90 5 87 80 7 5
3 94 89 5 86 81 5 5
silicone gel
wax
E1 91 87 4 75 64 11 5
2 95 82 3 93 80 13 5
3 95 93 2 91 82 9 5
Week 6
Comparative
Products
A1 93 92 1 83 80 9 5
2 95 93 2 92 80 12 5
3 95 81 14 89 74 15 5
B1 94 82 2 89 90 9 5
2 95 92 3 92 80 12 5
3 95 92 3 83 70 13 5
C1 96 92 4 90 75 15 5
2 95 92 3 83 77 10 5
3 94 89 5 87 69 18 5
D1 94 92 2 90 79 11 5
2 96 80 15 87 76 12 5
3 94 91 3 86 82 4 5
silicone gel
wax
E1 91 86 5 75 82 13 5
2 95 94 1 93 78 15 5
3 95 93 2 91 81 10 5
______________________________________


The silicone gel wax has been described as being a protectant for automobile paint, it is to be understood that it is also a suitable protectant for other painted finishes particularly such surfaces that are subjected to the weather and sunlight.

Evaluation of the Silicone Gel Protectant

The silicone gel protectant from example 3, was applied to portions of the vinyl and rubber surfaces on the interior and exterior of a new automobile. For comparison, a conventional "protectant" was also applied on portions of the vinyl and rubber surfaces on the interior and exterior of the automobile. The silicone gel wax was inspected visually. The silicone gel wax left a satin finish. In contrast, the conventional protectant appeared greasy, and left a visible mark when a finger was drawn across the surface. The silicone gel wax did not leave a visible mark when a finger was drawn across the surface.

Although one embodiment of this invention has been shown and described, various adaptations and modifications can be made without departing from the scope of the invention as defined in the appended claims.



(WO/2005/035631) AMINO-FUNCTIONAL SILICONE WAXES

* Biblio. Data
* Description
* Claims
* National Phase
* Notices
* Documents

* Note: OCR Text
o Note: Text based on automatic Optical
Character Recognition processes. Please
use the PDF version for legal matters

AMINO-FUNCTIONAL SILICONE WAXES The present invention concerns silicone waxes having plural tertiary or quaternary amino groups, their preparation and their use as softeners in the textile industry.

There is extensive literature on amino-functional silicone compounds. These compounds are used for example as plasticizers in the textile industry, as surface- treating agents, as thickeners or in the cosmetic industry. Nonetheless, there is a demand in the textile industry for softening substances which lead to products having a superior hand and which do not have the disadvantage of unstable emulsions in use.

It has now been found that certain silicone waxes having plural tertiary or quaternary nitrogen atoms can be processed into stable aqueous dispersions and have surprisingly good properties when used as softeners in the textile industry and lead to products having a pleasant, soft hand.

The invention accordingly provides amino-functional silicone waxes of the formulae (I) to (IV) where R is C11-C22-alkyl, linear or branched, R1 is C1-C7-alkyl or benzyl, preferably methyl or benzyl, R2 is-OH,-CH3,-OCH3,-OC2H5, A'is CH30SO3-, chloride, bromide, iodide or tosylsulfate, preferably CH30SO3-or chloride, n is 2 or 3, p is 10-200, preferably 20-50, q+z is 10-400, preferably 15-200, and q/z is 5-50, preferably 10-30.

These waxes, whether in the quaternized form (II) and (IV) or in the non-quaternized form (I) and (III), exhibit good properties when used as softeners. Their great advantage is that they can be used in the form of dispersions which, compared with emulsions, have a higher shearing force stability.

The present invention further provides for the preparation of the aforementioned silicone waxes. The initial step is to prepare fatty acid diamides by condensation of fatty acids, for example stearic acid or lauric acid, with diethylenetriamine or dipropylenediamine.

The resultant fatty acid diamide is reacted with silicone oils of the general formula (V) where p has the same meaning as in formula (I) or (II), to prepare the waxes of formula (I) or (II), or subsequently quaternized with the customary quaternizing agents such as methyl sulfate, ethyl sulfate, methyl halide, benzyl chloride or tosyl sulfate to prepare the waxes of the formula (II). The starting materials and their preparation will be known to one skilled in the art.

To prepare the waxes of the formula (III) or (IV), the resultant fatty acid diamide is reacted with silicone oils of the general formula (VI) where R2, (q+z) and q/z have the same meaning as in formula (III) or (IV), and to prepare the waxes of the formula (IV), the resultant fatty acid diamide is subsequently quaternized with the customary, aforementioned quaternizing agents.

The present invention further provides for the use of the aforementioned silicone waxes as softeners in the textile industry. The silicone waxes obtained can be converted by means of dispersants into aqueous dispersions which have a higher shearing force stability than emulsions and are very useful for softening textiles in that the material acquires a pleasant, soft hand.

EXAMPLES 1. Preparation of fatty acid diamides (Fatty acid: RCOOH) 1.1 Preparation of R-CONH (CH2) 2NH (CH2) 2NHCO-R 2 mol of fatty acid are heated to 105°C under nitrogen; 1 mol of diethylenetri- amine is then added dropwise while at the same time the temperature is raised to 130°C. This is followed by 24 hours of condensation at 130°C under a slow stream of nitrogen using a distillation bridge. The reaction mixture is subse- quently discharged. The acid number of the reaction mixture (number of mg of KOH to neutralize 1 g of product) is less than 7. The resultant amount of condensation product requires less than 1.1 mol of perchloric acid to titrate the free amino groups.

1.2 Preparation of R-CONH (CH2) 3NH (CH2) 3NHCO-R 1.1 is repeated using dipropylenediamine instead of diethylenediamine. Melting point of diamides (°C) Lauric acid Stearic acid Behenic acid Diethylenetri-110 118 123 diamide (Product D1) (Product D2) (Product D3) diamide Dipropylenetri-106 117 122 amine-1, 3- (Product D4) (Product D5) (Product D6) diacide 2. Preparation of silicone waxes 2.1 Silicone waxes W,-W6 661.5 parts of the silicone oil of the formula are reacted at 150°C under nitrogen for 14 hours with x parts of the diamides D to D6. A check is subsequently carried out to see that glycidyl groups are no longer present. The following waxes are obtained: Diamide x (parts) Silicone wax D1 233.5 W1 D2 317.5 W2 D3 373.5 W3 Da 247.5 W4 Ds 331.5 Ws De 387.5 We The waxes have the following structure : RCONH R-CO-NH NH-CO-R i Ha I H3 i H3 I Hzn -CH-CH-CH-0-Si--0-Si--0-Si-O-CHF-- H--.. 2 *f (i HZ) OH Z CH3 CH3 sz CH3 R-CO-NH NH-CO-R n = 2 or 3, R = C-C22 alkyl radical 2.2 Silicone waxes W7 - W12 661.5 parts of the silicone oil of the formula are reacted at 150°C under nitrogen for 14 hours with x parts of the diamides D to D6. A check is subsequently carried out to see that glycidyl groups have reacted quantitatively. The following waxes are obtained: Diamide x (parts) Silicone wax D1 230. 9 ? D2 313. 9 # W8 D3 369.3 W9 D4 244.7 W10 Ds 327.8 Wil De 383.2 Wi2 The waxes have the following structure: n = 2 or 3, R = C11-C22 alkyl radical 3. Preparation of quaternized silicone waxes WQ1 - WQ12 x parts of silicone wax W are melted and allowed to react with 25.2 parts of dimethyl sulfate for 2 hours at about 70-75°C. Silicone wax W WQo W x (parts) W1 358. 0 1 W2 391.6 2 W3 414.0 3 W4 363.6 4 W5 397.2 5 W6 419.6 6 W7 541.5 7 W8 591.9 8 W9 625.5 9 W10 549.9 10 W11 600.3 11 W12 633. 9 12 Waxes having the structures: and n = 2 or 3, R = C11-C21 alkyl radical are obtained.

4. Preparation of end products 4.1 Based on silicone waxes W,-W12 125.0 parts of silicone wax (W) are melted. 25.0 parts of a 70% solution of (dispersant 1) in propylene glycol and also 37.5 parts of stearyl poly-10-glycol ether (dispersant 2) are then added. As soon as there is a homogeneous melt, 800. 0 parts of water are added in increments with stirring. Finally, 12.5 parts of glacial acetic acid are added. This gives 1000.0 parts of a 12. 5% silicone wax dispersion (W-E).

4.2 Based on quaternary silicone waxes WQi-WQi2 4.1 is repeated except that the silicone waxes (WQ) are used instead of the silicone waxes (W) and 12.5 parts of water are added at the end instead of 12.5 parts of glacial acetic acid. This gives 1000.0 parts of a 12.5% silicone wax dispersion (WQ-E).

The products W1-E to W12-E and also WQ,-E to WQ12-E are very stable to shearing force; they can be applied to textile material (cotton and synthetic fibres) both in the padding process and in the exhaust process. The finished textile materials possess an excellent, soft, pleasant, smooth hand.

APPLICATION EXAMPLES The following finishing operations were carried out: Exhaust process The finished substrate is added to an aqueous liquor which, based on the substrate, contains 0.5% to 4.0% of the end products described in the examples, at about 40°C and a liquor ratio of 6: 1 to 20: 1, in a laboratory jet. After 20 minutes at pH 5.0 to 6.0 (40°C) and continuous agitation of the substrate, the substrate is removed from the liquor, whizzed and dried tensionlessly at 140°C for 70-90 seconds.

Padding process The finished substrate is padded at room temperature, to a 100% dry weight increase, with an aqueous liquor which contains 15 to 60 g/l of the end products W-E or WQ-E. The padded material is subsequently dried at 140°C for 70-90 seconds.

Substrate : Exhaust process: Tricot fabric, dyed, with or without setting - 100% cotton -polyester (50%)/cotton (50%) Padding process: Tricot or woven fabric, dyed, with or without setting - 100% cotton - polyester (50%) /cotton (50%) - polyester (100%) - polyacrylonitrile (100%) - nylon 6 (100%) Testing : Softness can be tested pairwise or using a handle-O-meter (for example a 211-5 Twing Albert). The finished samples are first conditioned (24 hours, 20°C, 65% relative humidity) before being assessed.

All the finishes show a distinct improvement in softness compared with unfinished fabric.

So GINA, is a carnuaba wax with amino functional silicones a wax or a sealant?

Regards
Bud Abraham

Wow ! Im lost. All I know is that the first car polish with silicone in it was Autobrite in 1947.

I believe this would depend on the percentage of either Carnauba or amino functional silicone in the specific product.

Hummm!!!! What was the point of the extensive post?

Wax typically has standard silicone fluids in it, not amino-functional silicones which are used in what are called sealants.

So the question still stands, if a wax has amino-functional silicones in the formulation is it a WAX or a PAINT SEALANT?

Has nothing to do with the amount of wax and/or sealant.

Regards

A question that will be debated for a long, long time.

The answer, in my opinion is closer to what Gina replied, "percentage".

That, plus what the "marketer" wishes to market a product as.

There are many mareketed "sealants", which contain a percentage of some sort of "wax", and don't use the amino's, but the dimethal's.

Many chemist will place a small percentage of a carnuaba, into their formulation of a "sealant" for various reasons.

1.To create a quick shine.
2.To aid in creating the observation by the end user of "beading", which many feel is the prime indicator of "protection".
3.To reduce the cost of production.
4.and "who knows" what else or the reasoning, but it happens.

Ketch

Thanks Ketch, I hoped you would jump in on this one. Not that this is an important issue or anything earth-shattering, just an interesting thought.

Your commentary I think explains the issue quite well.

Bud Abraham

Bud:

I posed your question to one of the industry’s eminent chemists, manufacturer and designer of protection products David Ghodoussi, Ph.D,CEO, Optimum Polymer Technologies, Inc and also Manufacturer Member of the NAPDR (National Association for Professional Detailing and Reconditioning

Here is his response.

As for the question of wax vs. sealant these terms are used interchangeably depending on how a product is being marketed. Majority of products in the marketplace contain a combination of one or more waxes, silicone fluids, and silicone sealants. Depending on the marketing approach some manufacturers claim non-silicone by using bodyshop safe silicones and others just refer to silicone oils as "shining agents." Let's also define what these refer too:

Waxes are natural substances (animal or vegetable) or synthetic materials solid at ambient temperature (20C.-25C.). They are insoluble in water, soluble in oils and are capable of forming a water repellant film. These include Carnauba wax(extract of Copemrica Cerifera), Candelilla wax (extract of Euphobies Cerifera and Pedilantus pavonis), and Alfa wax(extract of Stipa tenacissima), Montan wax, polyethylene wax, paraffin wax, oxidized paraffin wax, ozokerite, vegetable waxes such as olive tree wax, rice wax, hydrogenated jojoba wax or absolute waxes of flowers such as the essential wax of cassis flower; animal waxes such as beeswax, or modified beeswax (cerabellina).

Silicone oils also referred to as dimehtyl fluids are generally straight chain polydimethysiloxane fluids ranging in viscosity from 0.65 to 100,000 centipoises. The typical ones used in wax or sealants formulations however are between 350 to 10,000 centipoises viscosity. These have no reactivity and help with application or initial gloss. There are some modifications to improve characteristics of these oils by adding certain groups for instance aryl groups improve fire resistance and larger alkyl groups make silicone fluids bodyshop safe. Some manufacturers use these modified silicone fluids only to claim that the product does not contain silicone oils.

Sealants in general refer to amino-functional silicone oils or resins. An amino-functional polysiloxane contains highly polar pendant aminoalkyl modifying groups that enhance the durability of films formed by polysiloxanes, and promote adhesion of films to a variety of substrates. These include reactive and non-reactive, hydrolyzable and non-hydrolyzable derivatives.

Please feel free to use all or part of this if you feel this helps answer the question. Thank you.

Best Regards,
David Ghodoussi, CEO
Optimum Polymer Technologies, Inc.
Phone: (901) 363-4955
Fax: (901) 363-4956
“Member NAPDR working to improve the detail industry"

Talk about a wealth of information.

For a sealant to protect does it need to crosslink like Amino-Functional sealants do.

Bud-
In my opinion, "Carnauba" is a beautiful word but this natural wax is obsolete .
Zaino will equal the finest Carnauba waxes in shine and trouce them in durability .
Zaino resists harsh automatic car washes while such washes can remove a Carnauba wax .
Yeah, I know how Carnauba naturally protects the leaves on the trees in Brazil but if I owned those trees, I'd put Zaino on the leaves instead ( LOL) .

Right now, my short answer to any sealant or wax question is " Zaino ". www.zainostore.com

This is your car: ____ . This is your car on Zaino : ^^^***!!!!!
Any questions ?
Doug



Edited 1 time(s). Last edit at 08/01/2008 02:27PM by Doug Delmont.

An interesting thread for this part.

As for the question of wax vs. sealant these terms are used interchangeably depending on how a product is being marketed. Majority of products in the marketplace contain a combination of one or more waxes, silicone fluids, and silicone sealants. Depending on the marketing approach some manufacturers claim non-silicone by using bodyshop safe silicones and others just refer to silicone oils as "shining agents." Let's also define what these refer too:

Waxes are natural substances (animal or vegetable) or synthetic materials solid at ambient temperature (20C.-25C.). They are insoluble in water, soluble in oils and are capable of forming a water repellant film. These include Carnauba wax(extract of Copemrica Cerifera), Candelilla wax (extract of Euphobies Cerifera and Pedilantus pavonis), and Alfa wax(extract of Stipa tenacissima), Montan wax, polyethylene wax, paraffin wax, oxidized paraffin wax, ozokerite, vegetable waxes such as olive tree wax, rice wax, hydrogenated jojoba wax or absolute waxes of flowers such as the essential wax of cassis flower; animal waxes such as beeswax, or modified beeswax (cerabellina).

Silicone oils also referred to as dimehtyl fluids are generally straight chain polydimethysiloxane fluids ranging in viscosity from 0.65 to 100,000 centipoises. The typical ones used in wax or sealants formulations however are between 350 to 10,000 centipoises viscosity. These have no reactivity and help with application or initial gloss. There are some modifications to improve characteristics of these oils by adding certain groups for instance aryl groups improve fire resistance and larger alkyl groups make silicone fluids bodyshop safe. Some manufacturers use these modified silicone fluids only to claim that the product does not contain silicone oils.

Sealants in general refer to amino-functional silicone oils or resins. An amino-functional polysiloxane contains highly polar pendant aminoalkyl modifying groups that enhance the durability of films formed by polysiloxanes, and promote adhesion of films to a variety of substrates. These include reactive and non-reactive, hydrolyzable and non-hydrolyzable derivatives.

Please feel free to use all or part of this if you feel this helps answer the question. Thank you.

Best Regards,
David Ghodoussi, CEO
Optimum Polymer Technologies, Inc.
Phone: (901) 363-4955
Fax: (901) 363-4956
“Member NAPDR working to improve the detail industry"

David

Thank you for such an informative explanation on waxes, sealants and silicones.

As a chemist and an expert in the formulation of car care products can you please answer a couple of questions I have raised by some of the posts made on this forum:

1. What exactly is an "acrylic" sealant and, in your opinion, is it any different than most sealants?

2. Does or can wax cause scratches in paint or in any way harm the paint finish?

3. Is a sealant better to use on a paint finish than a wax? Or, why would one use a wax vs a sealant?

Thanking you in advance for your reply

Regards

Bud

You truly amaze me? First did you notice that this post was yours from 2008?
I ask you this? Do you want the real answer to your questions, or just someone to agree with you? Asking these same questions over and over is not going to give you the answer you want.