HK1166990B - Silicone modified fatty acids, method of preparation and usage thereof - Google Patents

Description

Silicone-modified fatty acids, method for the production and use thereof

Cross Reference to Related Applications

This application claims priority from U.S. application 61/239,215 filed on 9,2, 2009, which is incorporated herein by reference.

Technical Field

The present invention relates to silicone-modified fatty carboxylic acid compounds. More particularly, the present invention relates to low molecular weight, i.e., short chain, silicone-modified fatty carboxylic acids, their use, and methods of making the same.

Background

There is an increasing trend in the personal care, pharmaceutical and retail industries to use natural based products. The use of vegetable oils and waxes is well known in the art; however, they often have unpleasant sensory properties for personal care products. Accordingly, formulators often use low concentrations of these materials in their formulations. Formulators also often incorporate ingredients to enhance the sensory properties of skin care and hair care products. Silicones are a class of materials well known in the art for enhancing the sensory properties of personal care products. Typically, formulators can add vegetable oils or waxes and silicones separately to personal care products to achieve desired sensory requirements.

A variety of silicone-modified fatty carboxylic acids are known in the art. The preparation of these prior art compounds involves several methods, for example, a condensation reaction between a siloxane containing hydroxyl groups and the carboxyl groups of a fatty acid. Another commonly used method involves the hydrosilylation reaction of an olefin ester in the presence of a metal catalyst. Another prior art method uses an amino addition reaction of an amino modified siloxane to the carboxyl group of a fatty carboxylic acid. Examples of such compounds and reactions are disclosed, for example, in U.S. patent 5,051,489 to O' leick, jr, which discloses waxy, smooth solids prepared from silanol waxes for use in hair, skin, and textile compositions. The compounds of this patent are prepared by reacting silanol compounds with fatty carboxylic acids and/or polycarboxylic acids, esters or anhydrides. Another U.S. patent 5,136,063 to O' leick, jr. states a series of silicone fatty esters suitable for treating textiles and fibers. These compounds are prepared via a condensation reaction between a hydroxyl-containing siloxane polymer and a fatty carboxylic acid, ester or anhydride. U.S. patent 5,115,049 discloses fatty carboxylic acid salts of organofunctional siloxane amines. The synthesis of these compounds proceeds via an amino addition reaction in which the siloxane amine is neutralized by a fatty carboxylic acid. EP 0955340 discloses liquid silicone esters or blends prepared via hydrosilylation reactions for use in personal care and textile softening compositions. U.S. Pat. No. 4,912,242 discloses a method for preparing silicon esters by hydrosilylation of allyl esters using a metal complex catalyst. U.S. patent 4,725,658 to Thayer et al discloses silicone esters prepared by hydrosilylation of fatty esters rather than fatty acids.

Another disclosure of silicone modified fatty acids is U.S. patent 3,563,941, which states a silicone-carnauba copolymer synthesized by epoxy addition of epoxy group-containing siloxanes to the free hydroxyl groups present in carnauba wax. The method of this patent utilizes carnauba wax that contains unreacted hydroxyl groups. The hydroxyl groups react with the epoxy groups of the silicon-containing compound to form the silicone-carnauba wax copolymer.

However, in the present invention, it has been found that there are a number of benefits which can be obtained by first reacting a silicone with a fatty carboxylic acid and then introducing this material into the following composition: personal, hair and skin (i.e., cosmetic compositions), automotive, hard surface, or textile enhancing compositions.

It is therefore an object of the present invention to provide silicone-modified fatty carboxylic acids, i.e. silicone fatty esters, which are capable of imparting improved sensory feel on, for example, skin or hair.

Disclosure of Invention

The present invention provides a modified organosilicon compound comprising the reaction product of:

a) at least one cyclic ether silicone having the formula:

M_aM^A _bD_cD^B _dT_eT^C _fQ_g

wherein:

M＝R¹R²R³SiO_1/2

M^A＝R⁴R⁵R⁶SiO_1/2

D＝R⁷R⁸SiO_2/2

D^B＝R⁹R¹⁰SiO_2/2

T＝R¹¹SiO_3/2

T^C＝R¹²SiO_3/2；

Q＝SiO_4/2；

R¹、R²、R³、R⁵、R⁶、R⁷、R⁸、R¹⁰and R¹¹Each independently a monovalent hydrocarbon group having 1 to 6 carbon atoms; r⁴、R⁹And R¹²Each independently a monovalent hydrocarbon group containing 3 to 25 carbon atoms and having at least one epoxy group or oxetane group; wherein the subscript a,b. c, d, e, f and g are 0 or a positive number and their sum is no greater than 25, provided that at least one of subscripts b, d and f is a positive number; and the combination of (a) and (b),

at least one substantially pure aliphatic carboxylic acid.

The present invention also provides a process for preparing a modified organosilicon compound comprising:

i) reacting at least one cyclic ether silicone having the formula with at least one substantially pure aliphatic carboxylic acid in the presence of at least one catalyst:

M_aM^A _bD_cD^B _dT_eT^C _fQ_g

wherein:

M＝R¹R²R³SiO_1/2

M^A＝R⁴R⁵R⁶SiO_1/2

D＝R⁷R⁸SiO_2/2

D^B＝R⁹R¹⁰SiO_2/2

T＝R¹¹SiO_3/2

T^C＝R¹²SiO_3/2；

Q＝SiO_4/2；

R¹、R²、R³、R⁵、R⁶、R⁷、R⁸、R¹⁰and R¹¹Each independently a monovalent hydrocarbon group having 1 to 6 carbon atoms; r⁴、R⁹And R¹²Each independently a monovalent hydrocarbon group containing 3 to 25 carbon atoms and having at least one epoxy group or oxetane group; wherein the subscripts a, b, c, d, e, f and g are 0 or a positive number, andand not greater than 25, provided that at least one of subscripts b, d, and f is a positive number.

The novel fatty carboxylic acid modified silicones of the invention can, for example, improve the sensory feel on skin or hair, reduce viscosity and reduce color and odor relative to the starting fatty acids. These silicone-modified fatty acids, i.e., silicone fatty esters, can be added to cosmetic formulations in the form of emulsions, as blends with vegetable oils, and/or neat, and the like.

Detailed Description

Other than in the operating examples or where otherwise indicated, all numbers expressing quantities of materials, reaction conditions, durations, quantitative properties of materials, and so forth, used in the specification and claims are to be understood as being modified in all instances by the term "about".

It should also be understood that any numerical range recited herein is intended to include any sub-ranges within that range and any combination of the endpoints of such ranges or sub-ranges.

It should also be understood that any compound, material, or substance disclosed either explicitly or implicitly in the specification and/or recited in the claims as belonging to a collection of structurally, compositionally and/or functionally related compounds, materials, or substances includes both individual representatives of the collection and all combinations thereof.

It is also understood that the term "product" as used herein includes every possible use of any compound, material or substance explicitly or implicitly disclosed in the specification and/or recited in the claims, including, but not limited to, pharmaceuticals, medical formulations and/or compositions, skin creams, lotions, moisturizers, facial treatment products, facial cleansing products, body washes, colognes, powders, sunscreens, pre-shave lotions, after-shave lotions, liquid soaps, body washes, soap bars (bar soaps), shaving soaps, shaving foams, shampoos, hair conditioners, hair dyes, hair gels, mousses, styling products (manipulators), depilatories, nail polishes, make-up, color cosmetics, foundations, blushes, rouges, lipsticks, eyeliners, mascaras, eye shadows, oil removers (oil remotes), make-up removers, cosmetic removers, and/or the like, The delivery systems for oil and water soluble materials and the products for which these silicone containing compositions, mixtures or compounds are well known generally require the use of all the uses known in the art.

In each of the general structural chemical formulae described and/or claimed herein, wherein two or more substituents (including terms such as "group," "functional group," "group," and "moiety") are each defined as any one of several designated members, the formula should be construed to include all possible combinations of members defining all of these substituents (subclasses), and each combination (subclass) is considered disclosed as if it were individually listed.

The cyclic ether silicones of the invention which can be reacted with the aliphatic carboxylic acids are those which comprise epoxy-containing organic groups bonded to the silicon atom by a silicon-carbon bond. Epoxy groups are well known organic groups and examples of epoxy-containing organic groups useful in the present invention can be found in the literature, for example, see, U.S. Pat. No. 3,563,941, incorporated herein by reference in its entirety.

The cyclic ether-modified organosilicon compounds of the invention have the general formula:

M_aM^A _bD_cD^B _dT_eT^C _fQ_g

wherein:

M＝R¹R²R³SiO_1/2

M^A＝R⁴R⁵R⁶SiO_1/2

D＝R⁷R⁸SiO_2/2

D^B＝R⁹R¹⁰SiO_2/2

T＝R¹¹SiO_3/2

T^C＝R¹²SiO_3/2；

Q＝SiO_4/2；

R¹、R²、R³、R⁵、R⁶、R⁷、R⁸、R¹⁰and R¹¹Each independently a monovalent hydrocarbon group having 1 to 6 carbon atoms; r⁴、R⁹And R¹²Each independently a monovalent hydrocarbon group containing 3 to 25 carbon atoms and having at least one epoxy group or oxetane group; wherein subscripts a, b, c, d, e, f, and g are 0 or a positive number and their sum is no greater than 25, provided that at least one of subscripts b, d, and f is a positive number.

According to an embodiment of the present invention, the epoxy-modified silicone of the present invention (i.e., formula (1)), R¹、R²、R³、R⁵、R⁶、R⁷、R⁸、R¹⁰And R¹¹Each independently a monovalent hydrocarbon group having 1 to 3 carbon atoms. In another embodiment of the present invention, the epoxy-modified silicone of the present invention (i.e., formula (1)), R¹、R²、R³、R⁵、R⁶、R⁷、R⁸、R¹⁰And R¹¹Each independently a monovalent hydrocarbon group having 1 carbon atom. According to an embodiment of the invention, the sum of subscripts a, b, c, d, e, f and g of formula (1) is no more than 10. According to another embodiment of the present invention, subscript b is 0, subscript a is 2, subscripts c, e, and g are 0 or less than 3, and at least one of subscripts d and f is a positive number. According to yet another embodiment of the present invention, subscript b is 0, subscript a is 2, subscripts c, e, f, and g are 0, and d is 1. According to yet another embodiment, the present invention provides a personal care product comprising the modified silicone of the present inventionA compound and at least one personal care product ingredient. And further in accordance with yet another embodiment, the present invention provides a personal care product comprising the modified silicone compound of the present invention (free of silicone compounds prepared from sapucainha oil) and at least one personal care product ingredient.

Another embodiment of the present invention provides a pharmaceutical composition comprising a modified organosilicon compound of carboxylic acids derived from at least one cyclic organosilicon and sapucaine oil and at least one pharmaceutically acceptable carrier.

These cyclic ether organosilicon compounds can be prepared by the hydrosilylation reaction of an epoxy-functional olefin with a hydride-functional silicone. Examples may be found, for example, in U.S. Pat. nos. 4,083,856, 6,365,696 and 5,258,480, the entire contents of which are incorporated by reference into this application.

The following examples include, but are not limited to, cyclic ether organosilicon compounds useful in the present invention:

according to particular embodiments, particular cyclic ether organosilicon compounds useful in preparing the modified organosilicon compounds of the invention include the following:

1,1,1,3,5,5, 5-heptamethyl-3- [2- (7-oxa-bicyclo [4.1.0] hept-3-yl) -ethyl ] -trisiloxane;

1,1,3,3,5,5, 5-heptamethyl-1- [2- (7-oxa-bicyclo [4.1.0] hept-3-yl) -ethyl ] -trisiloxane;

1,1,1,3,5,5, 5-heptamethyl-3- [2- (1-methyl-7-oxa-bicyclo [4.1.0] hept-3-yl) -propyl ] -trisiloxane;

1,1,1,3,5,5, 5-heptamethyl-3-epoxyethylmethoxy-propyl-trisiloxane;

1,1,1,3,5,5, 5-heptamethyl-3- (ethyl-3-propoxymethyl-oxetanyl) -trisiloxane.

According to an embodiment of the present invention, the epoxy-functional silicone used herein has a number average molecular weight of 150g/mol to 2500 g/mol. According to another embodiment of the present invention, the epoxy-functional silicone used herein has a number average molecular weight of 100 to 150 g/mol. According to yet another embodiment of the present invention, the epoxy-functional silicone used herein has a number average molecular weight of 150g/mol to 300 g/mol.

The cyclic ether organosilicon compounds of the invention and the fatty carboxylic acids are reacted by a ring-opening addition reaction of the carboxyl groups on the fatty acids with the epoxy or oxirane groups of the cyclic ether organosilicon compounds. Since the fatty carboxylic acid contains a free acid group, i.e., -COOH, the silicone-modified fatty acid copolymer contains an ester linkage.

The amount of cyclic ether organosilicon compound used in the reaction is about stoichiometric equivalents, where up to 1 epoxy group is present per 1 carboxylic acid group, or a cyclic ether organosilicon/fatty acid stoichiometric ratio of about 1:1 to 1: 10.

Fatty acids relevant to the practice of the present invention include any fatty acid, i.e., a fatty carboxylic acid, which is an aliphatic monocarboxylic acid derived from or contained in an esterified form of an animal or vegetable fat, oil or wax. However, the fatty carboxylic acids of the present invention are considered to be substantially pure fatty carboxylic acids. The term "substantially pure" means that the fatty carboxylic acid used herein does not contain more than 5% of non-fatty carboxylic acid components. Exemplary non-fatty carboxylic acid components include, for example, triglycerides, ionic salts, non-functional hydrocarbons, solvents, and the like, which are not fatty acids described herein.

Natural fatty carboxylic acids typically comprise chains (typically unbranched, even limited) having from 2 to 34 carbon atoms, which may be saturated or unsaturated. However, larger fatty carboxylic acids are not common in nature or as synthetic materials (common).

According to an embodiment of the present invention, the fatty carboxylic acid used to prepare the modified organosilicon compounds of the invention is a hydrocarbon group containing at least one carboxylic acid group and having from 4 to 28 carbon atoms. The hydrocarbon group may be saturated or unsaturated. However, synthetic fatty acids having at least one carboxylic acid may be used herein.

Another embodiment of the present invention provides a pharmaceutical composition comprising a modified organosilicon compound according to the method of the invention derived from carboxylic acids of at least one cyclic organosilicon and sapucaine oil and at least one pharmaceutically acceptable carrier.

Illustrative examples of fatty carboxylic acids are oleic acid, linoleic acid, linolenic acid, palmitic acid, palmitoleic acid, myristic acid, stearic acid, hydnocarpic acid, cyclopentenoundecanoic acid, hydnocarpic acid, gallic acid, ricinoleic acid, behenic acid, malvalic acid, sterculic acid, 2-hydroxy-sterculic acid, and caprylic acid, and combinations thereof. According to another embodiment of the invention, the other fatty carboxylic acid is a fatty carboxylic acid comprising from about 12 to about 24 carbon atoms and at least one carbon-carbon double bond. In yet another embodiment, useful fatty carboxylic acids include, but are not limited to, the following: eleostearic acid, tall oil fatty acid, linseed oil fatty acid, tung oil fatty acid, safflower oil fatty acid, soybean oil fatty acid, and combinations thereof. Blends of fatty carboxylic acids may be used to prepare the modified organosilicon compounds of the invention. Examples of such blends include, but are not limited to, saponified olive oil, which typically comprises the ingredients listed in table a below. When the oil is saponified, the fatty carboxylic acid composition is similar in weight percent to the corresponding triglyceride in the masterbatch.

Table a:

free acid	0.3％
		Oleic acid triglycerides	78-83％
Polyunsaturated linoleic acid triglyceride	6-9％
		Saturated palmitic acid triglyceride	8-15％
Stearic acid triglyceride	1.5-3％

As is known in the art, natural fatty carboxylic acids can be prepared by saponifying triglycerides and removing glycerol as a by-product. However, synthetic fatty acids are typically prepared by oxidation of alpha-olefins.

Suitable catalysts for preparing the novel silicone-modified fatty acids of the present invention include, for example, tertiary amines, quaternary ammonium hydroxides, alkali metal hydroxides, and lewis acids such as boron trifluoride, tin tetrachloride, aluminum trichloride, and tetraisopropyl titanate. According to one embodiment of the invention, tetraisopropyl titanate is a catalyst for the preparation of silicone-modified fatty carboxylic acids.

The catalyst should be used in an amount of about 0.001 to 0.1 wt%, preferably about 0.001 to 0.01 wt%, of the total reactant components.

The reaction may also be carried out in a suitable organic solvent to reduce the reaction temperature. Suitable organic solvents include any neutral solvent that does not contain an active hydrogen, such as esters, ethers, ketones, hydrocarbons, tertiary amines, and amides. Examples of suitable organic solvents are pentane, isooctane, cyclohexane, methylcyclohexane, isohexane, n-heptane, n-octane, n-hexane, benzene, toluene, xylene, ethylbenzene, diethylbenzene, isobutylbenzene, petroleum ether, kerosene, petroleum essential oils, naphtha, etc., alone or in mixtures. It is generally preferred to use isopropanol as the organic solvent.

The compounds of the invention are preferably prepared by mixing an aliphatic carboxylic acid with an epoxy group-containing siloxane in the presence of a suitable catalyst. If desired, the solution may be heated, typically to about 80-90 deg.C, to reduce reaction time.

The physical appearance of the modified organosilicon compound compositions obtainable by the process of the invention can range from liquids to waxes, where the color is light to yellow. These silicones are easily incorporated into cosmetic products, and the benefits obtained in the formulation are spreading on the skin and/or hair, smooth and fine sensory feel.

The modified organosilicon compound compositions of the invention are of particular value in personal care products. In view of the unique characteristics of smoothness and sensory feel, these compositions can be used alone or blended with other personal care product ingredients to form a variety of personal care products.

Examples of personal care product ingredients include, but are not limited to, ester waxes, oils and fats of animal or vegetable origin, fatty alcohols, fatty acids, alkyl esters of fatty acids; hydrocarbon oils and waxes; water, organic solvents, perfumes, surfactants, oil-soluble vitamins, water-soluble vitamins, oil-soluble drugs, water-soluble drugs, actives, pharmaceutical compounds, and the like.

In particular, the modified organosilicon compound compositions of the invention are smooth and will improve the properties of the following products: skin care creams, lotions, moisturizers, facial treatment products such as pain killers or wrinkle removers, personal and facial cleansers, bath oils, perfumes, colognes, powders, sunscreens, pre-and post-shave lotions, liquid soaps, shaving foams and the like. They can be used in shampoos, hair conditioners, hair oils, hair waxes, hair sprays, mousses, styling products, depilatories, and nail polish and the like to improve gloss and dry time, and provide conditioning benefits.

In addition, the modified organosilicon compounds of the invention exhibit a variety of advantages and beneficial properties, such as clarity, storage stability, and ease of preparation. They have therefore found a wide range of applications, particularly in skin care, sunscreens, antiperspirants, deodorants, as carriers for perfumes, and hair softeners.

While the invention has been described with respect to essential features, reference is made to the following examples to illustrate further specific applications of the invention.

Various embodiments of the present invention are illustrated in the following examples, wherein all parts are by weight unless otherwise indicated.

Examples and comparative examples

Example 1 was prepared as follows: 65g of 1,1,1,3,5,5, 5-heptamethyl-3- [2- (7-oxa-bicyclo [4.1.0] hept-3-yl) -ethyl ] -trisiloxane are charged to a 250mL round-bottomed flask equipped with a stirrer, a condenser, a thermometer and a nitrogen sparge. 52 g of saponified chaulmoogra seed oil and 10mg of titanium (IV) isopropoxide were charged on the epoxy-modified siloxane. The mixture was heated to 120 ℃ and held under a slight nitrogen sparge for 6 hours (6H). At the end of the reaction, the product was cooled to ambient temperature and added to the tank. Completion of the reaction was assessed by epoxide titration.

Comparative example 2 was prepared as follows: 100.00g of the average structure was (C)₆H₉O)(CH₃)₂SiO[Si(CH₃)₂O]₂₀Si(CH₃)₂(C₆H₉O) and 75.15g of oleic acid were charged to a 250g round-bottom flask. The flask was blanketed with nitrogen and heated to 100 ℃. The flask was stirred with a magnetic stirrer. Titanium isopropoxide (0.5mL) was added and the flask was held at 100 ℃ for an additional 4 hours. The product was determined to be complete by titration to determine the consumption of the epoxy group. The product was a clear yellow viscous mass.

Comparative example 3 was prepared as follows: 100.29g of the average structure was (CH)₃)₃Si[OSi(CH₃)₂]₄₀[OSi(CH₃)(CH₂CH₂(C₆H₉O))]_11.5OSi(CH₃)₃The polydimethylsiloxane of (2) and 127.18g of oleic acid were charged to a 500g round-bottom flask. The flask was blanketed with nitrogen and heated to 100 ℃. The flask was stirred with a magnetic stirrer. Titanium isopropoxide (0.5mL) was added and the flask was held at 100 ℃ for an additional 4 hours. The product was determined to be complete by titration to determine the consumption of the epoxy group. The product was a clear yellow viscous mass.

Example 4 was prepared as follows: 45g of the average structure is (C)₆H₉O)(CH₃)₂Si(CH₃)₂O[Si(CH₃)_2.5O_1/2]₂The polydimethylsiloxane of (1) and 45g of saponified olive oil were charged into a 250g round-bottom flask. The flask was blanketed with nitrogen and heated to 100 ℃. The flask was stirred with a magnetic stirrer. Additive for foodTitanium isopropoxide (0.2mL) was added and the flask was held at 110 ℃ for an additional 6 hours. The product was determined to be complete by titration to determine the consumption of the epoxy group. The product was a clear orange to amber liquid.

Example 5 was prepared as follows: 43g of the average structure was (C)₆H₉O)(CH₃)₂Si(CH₃)₂O[Si(CH₃)_2.5O_1/2]₂The polydimethylsiloxane of (2) and 40g of saponified palm oil were charged to a 250g round bottom flask. The flask was blanketed with nitrogen and heated to 100 ℃. The flask was stirred with a magnetic stirrer. Titanium isopropoxide (0.2mL) was added and the flask was held at 110 ℃ for an additional 6 hours. The product was determined to be complete by titration to determine the consumption of the epoxy group. The product was a clear red to amber liquid.

The formulations of example 1 and comparative examples 2 and 3 are shown in tables 1 and 2 below:

table 1:

table 2:

the application comprises the following steps:

it is known to those skilled in the art that the perception of stickiness is directly related to both the viscosity and the surface tension of the formulation. Table 3 below lists the viscosity and surface tension of formulations A and D of example 1 and formulations B-C and E-F of comparative examples 2 and 3, respectively.

Table 3:

the application comprises the following steps:

the combination of the fatty acid modified silicone and the natural oil has a better sensory profile than the natural oil alone. Examples, comparative examples and formulations are shown in tables 4 and 5 below. Each formulation was tested for tackiness by a panel of 8 people. Each panelist applied an aliquot of each formulation to the underside of the arm. The substances were applied to the skin and the panelists evaluated each formulation for a rating of 1 to 5.1 is the least viscous and 5 is the most viscous.

Table 4:

	viscosity of
		Example 1	1
Comparative example 2	3
		Comparative example 3	3.8

Table 5:

	viscosity number
		Preparation A	1.0
Preparation B	2.0
		Preparation C	1.5
Cotton seed	1.2
		Preparation D	2.2
Preparation E	2.4
		Formulation F	2.4
Lanolin	3.6

Sensory test panel

Example 4 was blended with olive oil and tested by a panel of 5 people for greasiness, tack, gloss and spreadability. Each panelist smears an aliquot of each sample under the arm. The substances were applied to the skin and the panelists evaluated each formulation for a rating of 1 to 5.1 is the least viscous, greasy, glossy or spreadable, and 5 is the most preferred. The control was natural olive oil.

Example 5 was tested by a panel of 5 people for greasiness, gloss, tack and spreadability. The control was saponified palm oil. Each panelist applied an aliquot of example 5 and saponified palm oil to the underside of the arm. Each material was applied to the skin and the panelists evaluated each sample on a scale of 1 to 5.1 is the least viscous, greasy, glossy or spreadable, and 5 is the most preferred.

Results

Table 6 below shows the average rating of the 5-person sensory test panel tested for example 4 and its blends with olive oil. The amount of modified silicone in each formulation is expressed in weight percent. All formulations were liquid at room temperature. Table 7 below shows the average ratings of the 5-person sensory test panel tested on example 5 and saponified palm oil.

Table 6:

table 7:

average grade	Palm fatty acid	Palm siloxanes
			Greasiness property	4,4	3,6
Viscosity of	3,6	2,6
			Degree of gloss	2,8	4,0
Spreading ability	4,2	4,0

The results shown in table 6 show that the silicone fatty esters derived from olive oil have less greasiness and gloss than the control. A reduction in greasiness and gloss was observed for formulations containing higher levels of silicone fatty esters. The spreadability and viscosity of the natural olive oil are very close to the results observed for the blends comprising silicone fatty esters and olive oil and the pure concentration (pure concentration) of example 4 is tested. Furthermore, the sensory test panel found that example 4 had better skin absorbency than natural olive oil and provided a dry feel on the skin not observed with natural oil. Less odour was also perceived.

The results shown in table 7 show that example 5 has lower stickiness, greasiness and similar spreading ability compared to palm fatty acid. On the other hand, it is relatively glossy, which is often a desirable property for hair care applications. As observed in example 4, the silicone fatty esters derived from palm oil have better skin absorption than the natural oils and also exhibit less odor. Finally, the results of tables 6 and 7 demonstrate that the sensory feel on the skin can be adjusted by using different concentrations and types of silicone modified fatty acids.

Personal care formulation a comprising example 1 was prepared using the ingredients shown in table B below:

table B:

personal care preparation A (bath oil)

Personal care formulation a, containing example 1, was prepared as a representative bath oil formulation and prepared in a conventional and customary manner known in the art. Addition of example 1 to personal care formulation a reduced the stickiness and increased the spreadability of the formulation.

Personal care formulation B comprising example 1 was prepared using the ingredients listed in table C below: personal care embodiments

Preparation B

(Foundation cream)

Phase II

Propylene glycol 12.0

Pigment 10.0

56.0 parts of water

Phase III

Silsoft 148 siloxane 2.0

Example 12.0

Personal care formulation B was prepared as a representative foundation and prepared in a normal and conventional manner known in the art. In particular, phase I was heated to 65 ℃, then phase II was added and mixed well, followed by phase III and mixed well. Upon mixing, the formulation was cooled to 35 ℃. Addition of example 1 to personal care formulation B reduced rub-in time (rub in time) and formulation stickiness.

While the invention has been described with reference to a preferred embodiment, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the scope of the invention. It is intended that the invention not be limited to the particular embodiment disclosed as the best mode contemplated for carrying out this invention, but that the invention will include all embodiments falling within the scope of the appended claims. All references referred to herein are expressly incorporated by reference.

Claims (29)

1. A product comprising a product component and a modified organosilicon compound consisting of the reaction product of the reaction of:

a) at least one cyclic ether silicone selected from the group consisting of: 1,1,1,3,5,5, 5-heptamethyl-3- [2- (7-oxa-bicyclo [4.1.0] hept-3-yl) -ethyl ] -trisiloxane; 1,1,3,3,5,5, 5-heptamethyl-1- [2- (7-oxa-bicyclo [4.1.0] hept-3-yl) -ethyl ] -trisiloxane; bis-ethylcyclohexyl oxide polysiloxane; 1,1,1,3,5,5, 5-heptamethyl-3- [2- (1-methyl-7-oxa-bicyclo [4.1.0] hept-3-yl) -propyl ] -trisiloxane; 1,1,1,3,5,5, 5-heptamethyl-3-epoxyethylmethoxy-propyl-trisiloxane; and 1,1,1,3,5,5, 5-heptamethyl-3- (ethyl-3-propoxymethyl-oxetanyl) -trisiloxane; and

b) at least one substantially pure aliphatic carboxylic acid,

wherein the product ingredients comprise one or more personal care ingredients or one or more pharmaceutical ingredients.

2. The product of claim 1 wherein the fatty carboxylic acid is at least one member selected from the group consisting of: fatty carboxylic acids of natural origin and synthetic fatty carboxylic acids.

3. The product of claim 1 wherein the fatty carboxylic acid is a hydrocarbon group containing at least one carboxylic acid group and having from 2 to 34 carbon atoms.

4. The product of claim 1 wherein the fatty carboxylic acid is at least one member selected from the group consisting of: oleic acid, linoleic acid, linolenic acid, palmitic acid, palmitoleic acid, myristic acid, stearic acid, hydnocarpic acid, cyclopentenoundecanoic acid, hydnocarpenic acid, gallic acid, ricinoleic acid, behenic acid, malvalic acid, sterculic acid, 2-hydroxy-sterculic acid, and caprylic acid.

5. The product of claim 1, wherein the amount of cyclic ether organosilicon compound used in the reaction is a stoichiometric equivalent, with up to 1 epoxy group or oxetane group present per 1 carboxylic acid group.

6. The product of claim 1 wherein the amount of cyclic ether organosilicon compound used in the reaction is from 1:1 to 1:10 of cyclic ether organosilicon/fatty acid stoichiometric ratio.

7. The product of claim 1, wherein the product ingredient is a personal care ingredient comprising a component selected from the group consisting of fatty alcohols, fatty acids, alkyl esters of fatty acids; hydrocarbon oils and waxes; water, organic solvents, perfumes, surfactants, skin creams, lotions, moisturizers, acne or wrinkle removers, personal and facial cleansers, bath oils, face powders, sunscreens, soaps, shaving foams, shampoos, hair conditioners, mousses, styling products, depilatories, and nail polishes.

8. The product of claim 1, wherein the product ingredient is at least one selected from the group consisting of: oils and fats of animal or vegetable origin, fatty alcohols, fatty acids, alkyl esters of fatty acids, hydrocarbon oils and waxes, organic solvents, surfactants, oil-soluble vitamins, water-soluble vitamins, oil-soluble drugs, water-soluble drugs, actives, pharmaceutically acceptable carriers and pharmaceutical compounds.

9. The product of claim 8 wherein the pharmaceutically acceptable carrier is water.

10. The product of claim 7 or 8 wherein the wax is an ester wax.

11. A product comprising the modified silicone compound of claim 1 selected from the group consisting of pharmaceutical compositions and delivery systems for oil and water soluble materials.

12. The product of claim 11, wherein the pharmaceutical composition is a medical composition for pharmaceutical purposes.

13. A process for preparing the product of claim 1 comprising the steps of:

(a) providing a modified organosilicon compound comprising reacting at least one cyclic ether silicone with at least one substantially pure aliphatic carboxylic acid in the presence of at least one catalyst; the cyclic ether silicone is at least one selected from the group consisting of: 1,1,1,3,5,5, 5-heptamethyl-3- [2- (7-oxa-bicyclo [4.1.0] hept-3-yl) -ethyl ] -trisiloxane; 1,1,3,3,5,5, 5-heptamethyl-1- [2- (7-oxa-bicyclo [4.1.0] hept-3-yl) -ethyl ] -trisiloxane; bis-ethylcyclohexyl oxide polysiloxane; 1,1,1,3,5,5, 5-heptamethyl-3- [2- (1-methyl-7-oxa-bicyclo [4.1.0] hept-3-yl) -propyl ] -trisiloxane; 1,1,1,3,5,5, 5-heptamethyl-3-epoxyethylmethoxy-propyl-trisiloxane; and 1,1,1,3,5,5, 5-heptamethyl-3- (ethyl-3-propoxymethyl-oxetanyl) -trisiloxane; the catalyst is selected from tertiary amines, quaternary ammonium hydroxides, alkali metal hydroxides and lewis acids; and

(b) combining the modified organosilicon compound and at least one personal care ingredient or at least one pharmaceutical ingredient.

14. The method of claim 13, wherein the fatty carboxylic acid is at least one member selected from the group consisting of: fatty carboxylic acids of natural origin and synthetic fatty carboxylic acids.

15. The method of claim 13, wherein the fatty carboxylic acid is a hydrocarbon group comprising at least one carboxylic acid group and having 2 to 34 carbon atoms.

16. The method of claim 13, wherein the fatty carboxylic acid is at least one member selected from the group consisting of: oleic acid, linoleic acid, linolenic acid, palmitic acid, palmitoleic acid, myristic acid, stearic acid, hydnocarpic acid, cyclopentenoundecanoic acid, hydnocarpenic acid, gallic acid, ricinoleic acid, behenic acid, malvalic acid, sterculic acid, 2-hydroxy-sterculic acid, and caprylic acid.

17. The process of claim 13, wherein the catalyst is at least one member selected from the group consisting of: tin tetrachloride, aluminum trichloride, and tetraisopropyl titanate.

18. The process of claim 13 wherein the amount of catalyst is from 0.001 to 0.1 weight percent of the total reactant components.

19. The process of claim 13 wherein the catalyst is from 0.001 to 0.01 weight percent of the total reactant components.

20. The process of claim 13, wherein the amount of cyclic ether organosilicon compound used for the reaction is a stoichiometric equivalent, with up to 1 epoxy group or oxetane group present per 1 carboxylic acid group.

21. The method of claim 13, wherein the amount of cyclic ether organosilicon compound used for the reaction is from 1:1 to 1:10 cyclic ether organosilicon/fatty acid stoichiometric ratio.

22. The product of claim 1, wherein the product ingredient is a pharmaceutical ingredient.

23. A product comprising a product component and a modified organosilicon compound consisting of the reaction product of the reaction of:

a) at least one cyclic ether silicone selected from the group consisting of: 1,1,1,3,5,5, 5-heptamethyl-3- [2- (7-oxa-bicyclo [4.1.0] hept-3-yl) -ethyl ] -trisiloxane; 1,1,3,3,5,5, 5-heptamethyl-1- [2- (7-oxa-bicyclo [4.1.0] hept-3-yl) -ethyl ] -trisiloxane; bis-ethylcyclohexyl oxide polysiloxane; 1,1,1,3,5,5, 5-heptamethyl-3- [2- (1-methyl-7-oxa-bicyclo [4.1.0] hept-3-yl) -propyl ] -trisiloxane; 1,1,1,3,5,5, 5-heptamethyl-3-epoxyethylmethoxy-propyl-trisiloxane; and 1,1,1,3,5,5, 5-heptamethyl-3- (ethyl-3-propoxymethyl-oxetanyl) -trisiloxane; and

b) at least one substantially pure aliphatic carboxylic acid,

wherein the product ingredients comprise one or more pharmaceutical ingredients and the product comprises at least one pharmaceutically acceptable carrier and a modified silicone compound, wherein the at least one substantially pure fatty carboxylic acid is derived from sapucaine oil.

24. The method of claim 13, wherein the at least one substantially pure fatty carboxylic acid is derived from sapucaine oil.

25. The product of claim 1, wherein the at least one substantially pure fatty carboxylic acid used to prepare the modified silicone is selected from the group consisting of oleic acid, linoleic acid, linolenic acid, palmitic acid, palmitoleic acid, myristic acid, stearic acid, hydnocarpic acid, cyclopentene undecanoic acid, hydnocarpic acid, gallic acid, ricinoleic acid, behenic acid, malvalic acid, sterculic acid, 2-hydroxy-sterculic acid, caprylic acid, elaeostearic acid, tall oil fatty acid, linseed oil fatty acid, tung oil fatty acid, safflower oil fatty acid, soybean oil fatty acid, and combinations thereof.

26. The method of claim 13, wherein the carboxylic acid is selected from the group consisting of oleic acid, linoleic acid, linolenic acid, palmitic acid, palmitoleic acid, myristic acid, stearic acid, hydnocarpic acid, cyclopentenoundecanoic acid, hydnocarpic acid, gallic acid, ricinoleic acid, behenic acid, malvalic acid, sterculic acid, 2-hydroxy-sterculic acid, caprylic acid, elaeostearic acid, tall oil fatty acid, linseed oil fatty acid, tung oil fatty acid, safflower oil fatty acid, soybean oil fatty acid, and combinations thereof.

27. The product of claim 1, wherein the substantially pure fatty carboxylic acid is derived from olive oil or palm oil.

28. The method of claim 13, wherein the substantially pure fatty carboxylic acid is derived from olive oil or palm oil.

29. The product of claim 7 wherein said styling product is selected from the group consisting of hair oils, hair waxes, and hair gels.