A guidance system for internally controlling the flight path of a missile includes a guidance platform having dispersion control means mounted on the guidance platform for detecting acceleration of the missile due to lift and side forces. The dispersion control means includes dispersion detection means to calculate the velocity and position errors relative to a drag-only trajectory from the detected acceleration due to the lift and side forces. The internal guidance system also includes missile positioning means for controlling the position of the missile platform to substantially eliminate the velocity and position errors. The guidance system also includes level finding means for determining a substantially horizontal level axis and the orientation of the missile relative to a level axis. The missile positioning means also performs other functions such as missile leveling in which the wings-level axis of the missile is aligned to the level axis. Accordingly, the position of a free-falling missile may be internally controlled to increase the targeting accuracy of the missile without initialization of the missile from the launch platform.

For many years, aircraft have deployed missiles during flight. The missiles have principally been designed to contact a target on the ground, i.e., an air-to-surface missile, or in the air, i.e., an air-to-air missile. In an attempt to control the flight of the missiles, various guidance systems and methods have been developed.
Initially, missiles were unguided and simply dropped from aircraft during flight. The missiles would then free-fall to earth subject to the prevailing gravitational and aerodynamic forces. Thus, following the missile's deployment, the flight pattern of the missile was not controlled. Accordingly, the accuracy with which such missiles contacted the target was relatively low since, even though the crew deploying the missile would generally consider the speed of the aircraft and any known wind conditions in selecting the deployment coordinates for the missile, the missile was subject to numerous unknown sources of error.
The inability to control the flight path of a deployed missile and to correct for errors introduced by unknown sources, such as intermittent high-level wind currents, was unsatisfactory. For example, even a missile which misses its target by only a small distance may either be totally ineffective or may cause inadvertent harm. In either event, however, the missile would have been unnecessarily expended and the target would remain unscathed.
Numerous modern missile applications prefer to launch missiles from remote locations, i.e., locations located many thousands of feet both vertically and horizontally from the intended target, in order to avoid detection or possible retaliation. Missiles capable of such remote deployment are considered to have a long "stand off". The launch of missiles from remote locations further exacerbates the targeting deficiencies of unguided missiles due to the increased duration of the sources of error acting upon the missile during its extended flight from its deployment to the target.
In an attempt to control the flight path of missiles, inertial guidance systems have been placed onboard some missiles. Initialization of such inertial guidance systems is required prior to launch of the missiles. For example, guidance system alignment and target information, such as the coordinates of the launch and target locations is typically downloaded from the launch platform, such as an airplane, via a data interface to the missile prior to launch. Following launch, the onboard guidance system controls the flight path of the missile via the missile's external control surfaces to effectively steer the missile from the launch coordinates to the target coordinates while compensating for external forces.
Such onboard guidance systems typically require the deploying aircraft to be equipped with fire control avionics to download the proper data to the missile prior to its launch. In addition, an appropriate interface between the aircraft avionics and the guidance system of the missile is required. Therefore, the number of properly equipped aircraft and aircraft weapon stations from which such missiles may be launched is limited. In addition, while fire control avionics and an appropriate interface could be added to more aircraft, the cost of the aircraft modifications would be prohibitive.
Another attempt to provide increased accuracy for guided missiles employs sensor systems, such as radar, on the missiles. These missiles are typically referred to as terminal homing missiles. The sensor system of the missile searches for a designated target, and upon recognition of the designated target, controls the flight of the missile such that it impacts upon the target.
Although missiles with inertial guidance and/or terminal homing have improved the accuracy with which targets may be attacked, these missiles typically require expensive electrical and data interfaces with their air or ground launch platforms or complex sensor systems. Thus, it would be desirable to have a missile guidance system that did not require a launch platform to be equipped with an expensive or complex electrical and data missile interface and did not require a complex sensor system.

Self-initializing internal guidance system and method for a missile


A fast-drying coating composition intended primarily as an automotive clear coat contains

This invention relates to a curable coating composition particularly adapted for use as a clear top coat on automobiles to provide fast drying speed. More particularly, the type of coating involved is that which includes as the primary binder constituents an acrylic polyol and a curing agent, typically a polyisocyanate.
Automobiles are sometimes coated with a plurality of layers, typically a pigmented base coating composition onto which is subsequently applied a different top coating composition. The top coat is frequently referred to as xe2x80x9cclear,xe2x80x9d that is, substantially without pigment, but minor amounts of pigments or other materials that affect the appearance of the automobile may be included. Acrylic polyol based top coatings are particularly useful for their compatibility with a wide variety of base coating compositions.
A major factor in the productivity of an automobile painting operation is the speed with which the top coat dries to a condition that is no longer tacky. xe2x80x9cDryingxe2x80x9d in this context does not entail completing the curing reactions, but rather an initial surface hardening due primarily to solvent evaporation. Although acrylic polyol based coating compositions have a desirable combination of properties, it has been desired to shorten the dry time of this type of coating. It was known to increase drying speed by selecting monomers that increase the Tg (glass transition temperature) of the acrylic polyol. In particular, increasing the methacrylate monomer content of the acrylic polyol was known as a way to increase Tg (U.S. Pat. Nos. 5,279,862 and 5,324,953). Attempts to further increase drying speed, especially under ambient conditions, have heretofore not been as successful as desired because increased drying speed was generally been accompanied by an undesirable degradation in the appearance of the final coating. It is therefore an objective of the present invention to shorten drying times of the acrylic polyol/isocyanate type of coating composition while continuing to provide the other properties required of automotive applications.
French Patent Publication No. 2 452 500 discloses generally the use of glycidyl compounds reacted with acrylic acid or methacrylic acid as a component of acrylic polyols.
The rapid-drying coating composition of the present invention contains as the primary binder components (A) 50 to 80 weight percent of an acrylic polyol more fully described below, and (B) 20 to 50 weight percent of a curing agent reactive with hydroxyl groups, such as a polyisocyanate. The weight percentages are based on the total resin solids weight of (A) plus (B). The particular acrylic polyol of (A) is the free radical reaction product of vinyl monomers, of which 0.5 to 15 percent by weight (based on total resin solids weight of the monomer mixture from which acrylic polyol A is made) is an acrylic compound having the structure:
where R1=H or CH3,
R3 is H or an alkyl group,
R4 is an alkyl group, and
R5 is an alkyl group containing at least four carbon atoms.
The coating composition of the present invention comprises two components that are maintained as separate packages until immediately prior to use. One component (A) contains acrylic polyol, and the other component (B) contains a curing agent reactive with the hydroxyl groups in the first component. Preferably, the curing agent includes a polyisocyanate, but may comprise other known curing agents reactive with hydroxyl groups such as melamine-formaldehyde compounds and anhydrides. The reaction product of components (A) and (B) comprises the primary film-forming portion of the coating composition. Optimized commercial embodiments of the coating composition may optionally include additional ingredients such as diluents (e.g., solvents and/or reactive resinous diluents), catalysts, ultraviolet light absorbers or stabilizers, and pigments as are conventional in the art. These additional ingredients may be included in either or both components. Such acrylic based coating compositions are particularly useful for automotive finishes, especially as clear top coats over a pigmented base coat. The clear coatings are very advantageous as clear coats over a variety of base coats. In a particular commercial application of the present invention, the coating composition is intended for use in refinishing automobiles, wherein drying of the film-forming polymer is effected at or near ambient temperatures.
The acrylic polyol is made by addition polymerization of at least two types of unsaturated monomers, at least one of which includes the structure (I) above. Preferably, additional hydroxyl functionality is provided by including in the monomer mixture another monomer having a hydroxyl group. Most commonly, several other monomers are included to provide desired physical properties to the final coating.
Based on total resin solids weight of the monomer mixture, the acrylic polyol of the present invention may be synthesized from a monomer combination that comprises: (a) 0.5 to 15 weight percent of a compound of structure (I); (b) 0 to 45 weight percent hydroxy-containing unsaturated monomers such as hydroxyalkyl acrylates and methacrylates; and (c) from 40 to 98 weight percent of other ethylenically unsaturated copolymerizable materials such as non-functional alkyl acrylates, alkyl methacrylates, and vinyl aromatic monomers. The preferred weight percentages of these monomers are 1 to 10 percent of (a), 20 to 40 percent of (b), and 50 to 80 percent of (c).
The monomer (a), i.e., the compound of structure (I), comprises an acrylate or methacrylate in which the esterifying group is the residue of a glycidyl group which is, in turn, bound to a terminal group that includes a branched alkyl group, preferably a tertiary alkyl group. At least one of the alkyl branches in the terminal group may include a chain four or more carbon atoms in length. Preferably the branched alkyl group includes at least eight carbon atoms. A branched alkyl structure in the terminal group is believed to be particularly advantageous for attaining optimal results with the present invention. Surprisingly, the substantial chain length of monomer (a) and its inclusion of alkyl groups of substantial length permit the acrylic polyols into which it is polymerized to have very rapid drying rates without a substantial loss of hardness in the final coating that might otherwise be expected of such a structure. Good gloss and flow properties are also attained with the preferred embodiments.
Monomer (a) may be synthesized by reacting acrylic or methacrylic acid with a monoepoxide having substantial hydrocarbon chain length, such as commercially available epoxidized alpha olefins of the formula:
where R6 includes a branched alkyl group having at least 6 carbon atoms, preferably at least 8 carbon atoms. Polyepoxies such as certain of the commercially available family of EPON products may be used if partially defunctionalized to form monoepoxies. Epoxies with little or no aromatic content are preferred for automotive coatings. Preferably, the terminal group in the esterifying group of monomer (a) itself includes an ester group, in which case the monomer may be the reaction product of acrylic acid or methacrylic acid and CARDURA E (a glycidyl ester of Versatic acid sold by Shell Chemical Company). Versatic acid is a proprietary, synthetic blend of isomers of saturated tertiary alkyl monoacid having nine to eleven carbon atoms. The (meth)acrylic and CARDURA E reaction yields the following structure:
where the groups are as defined above. Alternatively, monomer (a) with an ester-containing terminal group may be produced from the reaction of glycidyl acrylate or glycidyl methacrylate with a long chain organic acid such as Versatic acid, neodecanoic acid, or isostearic acid. The branched structures of the preferred acids are believed to be advantageous.
Examples of suitable hydroxy-containing unsaturated monomers of group (b) in the monomer mixture employed to make acrylic polyol (A) are vinyl monomers such as hydroxyalkyl acrylates and methacrylates, including the acrylic acid and methacrylic acid esters of ethylene glycol and propylene glycol. Typically, these acrylates and methacrylates have 2 to 6 carbon atoms in the alkyl group. Also useful are hydroxy-containing esters and/or amides of unsaturated acids such as maleic acid, fumaric acid, itaconic acid and the like.
Monomers of group (c) in the monomer mixture include a wide range of unsaturated compounds. Preferably the major portion of the group (c) monomers are vinyl monomers, more specifically alkyl, cycloalkyl, or aryl acrylates and methacrylates having 2 to 6 carbon atoms in the esterifying group. Examples of particularly useful monomers are methyl methacrylate and n-butyl methacrylate. Other monomers that may be considered useful include lauryl methacrylate, 2-ethylhexyl methacrylate, isobornyl methacrylate, and cyclohexyl methacrylate. An aromatic vinyl monomer frequently included is styrene. Other copolymerizable monomers which may optionally be included in the group (c) monomers are ethylenically unsaturated materials such as monoolefinic and diolefinic hydrocarbons, unsaturated esters of organic and inorganic acids, amides and esters of unsaturated acids, nitriles, and unsaturated acids. Examples of such monomers include 1,3-butadiene, acrylamide, acrylonitrile, alpha-methyl styrene, alpha-methyl chlorostyrene, vinyl butyrate, vinyl acetate, allyl chloride, divinyl benzene, diallyl itaconate, triallyl cyanurate. It should be understood that monomer group (c) may include mixtures.
In addition to the film-forming components, other adjuvant resins such as polyesters can also be added to the formulation of the composition of the present invention. Usually, these polyesters are polyester polyols which are designed to be cured with a polyisocyanate. The polyesters are formed by the polyesterification of an organic polycarboxylic acid or its functional equivalent thereof with an organic polyol. Among the acids which can be used are phthalic acid, terephthalic acid, tetrahydrophthalic acid, hexa-hydrophthalic acid, azelaic acid and dimerized fatty acid including mixtures. Examples of suitable polyols are ethylene glycol, 1,4-butanediol, neopentyl glycol, trimethylpentanediol and trimethylolpropane including mixtures. Also, polycaprolactone-type polyesters may be employed which are formed from reaction of a cyclic lactone such a epsilon-caprolactone with a polyol or a hydroxy acid such as ethylene glycol and dimethylolpropionic acid.
In the practice of preferred embodiments of the invention, the curing agent of component (B) comprises a polyisocyanate curing agent which is capable of reacting with the active hydrogens in the acrylic polyol to give a thermosetting coating. A combination of two or more polyisocyanates is sometimes found to be useful.
Examples of polyisocyanates that may be used in component (B) are aliphatic, cycloaliphatic, and aromatic polyisocyanates, including mixtures thereof. Typically, the polyisocyanate is a diisocyanate, preferably an aliphatic isocyanate. Examples of suitable aliphatic diisocyanates include 1,4-tetramethylene diisocyanate and 1,6-hexamethylene diisocyanate. Examples of suitable aromatic diisocyanates are 4,4xe2x80x2-diphenylmethane diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate and toluene diisocyanate. Examples of suitable cycloaliphatic diisocyanates include 1,4-cyclohexyl diisocyanate, isophorone diisocyanate, 4,4xe2x80x2-methylene-bis-(cyclohexyl isocyanate). Triisocyanates such as TMXDI-IMP aliphatic triisocyanate available from Cytec Industries, Inc., can also be used. Isocyanurates and biurets of the diisocyanates described above can also be used. Preferably, the polyisocyanate curing agent of the present invention is an isocyanurate, such as the isocyanurate of hexamethylene diisocyanate, or blend of isocyanurates.
The amounts of acrylic polyol and polyisocyanate curing agent which are used in the practice of the invention are preferably adjusted so that the equivalent ratio of isocyanate groups to hydroxyl groups is within the range of 0.8:1 to 1.5:1, preferably slightly greater than 1:1. Isocyanate to hydroxyl equivalent ratios greater than this ratio are not preferred because hardness and durability of the resultant coating may suffer; whereas ratios lower than this ratio are not preferred because flexibility of the resultant coating may suffer.
Also present in preferred embodiments of the compositions intended for automotive coatings are constituents to resist the affect of solar ultraviolet radiation. These include ultraviolet light stabilizers and ultraviolet light absorbers, and preferably both are included. When they are included, effective amounts of ultraviolet light stabilizers and absorbers are each typically in the range of 0.01 to 5.0 percent by weight, preferably 1.5 to 2.5 percent by weight, the percentages based on the total weight of solids of the curing composition. A variety of ultraviolet light stabilizers well known to those skilled in the art can be used. Especially useful are the UV stabilizers and absorbers commercially available under the name TINUVIN(copyright) from Ciba-Geigy Company.
When formulated as automotive refinish coatings, the compositions of the present application include organic liquid diluent, typically in an amount of between 10 to 60 percent by weight of the total composition. Additional liquid diluent is commonly added at the point of use in the form of a viscosity reducer in accordance with the particular equipment and conditions at the paint shop, which may further increase the total solvent content. By liquid diluent is meant a volatile solvent or non-solvent which is removed after the coating is applied and which reduces viscosity sufficiently to permit control of coating thickness, flow, uniformity, and appearance in whatever coating application technique (viz., spraying) is used. Also, diluents assist in substrate wetting, resinous component compatibility, package stability, and coalescence or film formation. Examples of suitable diluents include aromatic hydrocarbons such as toluene and xylene, ketones such as methyl ethyl ketone and methyl isobutyl ketone.
Metal catalysts are used in the coating compositions of present invention for facilitating the cure of compositions containing hydroxyl and isocyanate groups. Preferably, the metal catalysts are formed from tin, cobalt, calcium and cesium, preferably from tin. Such metal catalysts are known in the art for accelerating the reaction of hydroxyl-containing organic molecules with isocyanates to form urethane groups. Representative of such catalysts are metal salts of carboxylic acids, diorganometallic oxides, mono- and diorganometallic carboxylates, and the like. Specific examples of such metal catalysts are calcium naphthanate, cesium naphthanate, cobalt naphthanate, dibutyl tin dilaurate, dibutyl tin diacetate, dibutyl tin octoate and dibutyl tin naphthanate. Such catalysts are used in curing polyisocyanate-polyol compositions in an amount selected to provide the particular performance level desired, and may range from 0 to 0.10 percent by weight of the solids content of such compositions. In preferred commercial embodiments, the amount of metal catalyst of the type disclosed above is typically in the range of 0.05 to 5.0 percent, the percentages based on the total weight of the solids of the curing compositions.
The film-forming compositions of the present invention are particularly adapted to be formulated into clear coating compositions. However, they could be formulated with pigments to form pigmented coating compositions. The pigments may be any of the conventional types comprising, for example, iron oxides, lead oxides, strontium chromate, carbon black, coal dust, titanium dioxide, talc, barium sulfate, as well as color pigments such as cadmium yellow, cadmium red, chromium yellow and metallic pigments such as aluminum flake. The pigment content of the paint is usually expressed as the pigment-to-resin weight ratio. In the practice of the invention, when the film-forming coating compositions of the present invention contain a pigment, the pigment-to-resin weight ratios may be as high as 2:1 and for most pigmented coatings are within the range of 0.05 to 1:1.
The coating compositions of the present invention dry rapidly, with dust-free times of 15 to 20 minutes or less being attainable. Determination of dust-free time is described in the examples. Tack-free times (determined by thumb pressure) of some embodiments are on the order of 60 minutes to 75 minutes. The final films are smooth, flexible, hard, and durable. The coating compositions are particularly useful for application over a variety of aqueous and non-aqueous pigmented basecoats, both thermoplastic and thermosetting. Because of their fast drying rate, they are especially useful in automotive refinish applications.
The invention is further illustrated by the specific embodiments set forth in the examples. Examples 1 through 4 present a comparison of the invention with a composition disclosed in French Patent Publication No. 2 452 500. Example 1 relates to an acrylic polyol of the present invention, while Example 2 is a reproduction of an acrylic polyol in the French patent publication. Examples 3 and 4 are isocyanate-cured, two component coating compositions that include the acrylic polyols of Examples 1 and 2, respectively. The dust-free times reported in Table 1 demonstrate the superior dry speed of the present invention relative to the approach in the French patent. Example 5 is a preferred embodiment of a automotive refinish composition in accordance with the present invention, which includes the acrylic polyol of Example 1. All compositional values in the examples are in parts by weight unless indicated otherwise.

Abstract: (A) 25 to 80 weight percent of an acrylic polyol which is the polymerization product of unsaturated monomers of which 0.5 to 15 percent by weight (based on resin solids weight of the monomers) is an acrylate having the structure:

Abstract: where R1=H or CH3,

Abstract: R3 is H or an alkyl group, R4 is an alkyl group, and R5 is an alkyl group containing at least four carbon atoms; and

Abstract: (B) 20 to 75 weight percent of a curing agent reactive with hydroxyl groups, particularly polyisocyanates.


An improved golf club head is disclosed, in which a desired weight for the head is precisely controlled by installing into a cavity formed in the rear wall of the club head""s hollow main body a selected weight cartridge from a group of such cartridges having identical sizes but a range of weights. The selected weight cartridge is installed simply by sliding it into the rear wall cavity, where it is retained by a snap fit, and/or by an interference fit, and/or by a suitable bonding material, without the need for a screw attachment. This greatly simplifies the golf club head""s manufacture, thus reducing its cost. The invention is applicable to golf club heads of all kinds, including metal woods, irons and putters.

This invention relates generally to golf club heads and to methods for making them and, more particularly, to golf club heads and related methods in which the club head incorporates an added weight component to provide the head with a desired weight.
One important parameter of golf clubs is the weight of their heads, which must be carefully controlled, not only to meet the particular needs of the individual golfer using the club, but also to combine with the golfer""s other clubs to form a matched set. Golf club manufacturers, therefore, customarily weigh each club head during the manufacturing process and add one or more components of precise weight so as to adjust the club head""s weight to a desired overall value.
The added components for adjusting the club head""s weight have taken many different forms. One common form, which has been used with metal wood-type golf club heads, is a material such as epoxy that is added in selected amounts to the club head""s hollow cavity. Although this use of epoxy has been generally effective in correcting for weight variances in golf club heads, negative side effects can result. For example, the epoxy can affix to the inner surface of the club head""s ball-striking face, which can have adverse effects, such as lowering the face""s coefficient of restitution. Also, pooling of the epoxy can displace the club""s center of gravity, and can affect the club head""s sound at ball impact, in an indeterminate way.
Another common form for the added weight component has been a metallic plug installed into the hollow shaft of the club, where it joins to the club head""s hosel. Although generally effective in providing the club head with the desired weight, such metallic plugs sometimes can loosen and cause undesired rattling during the club""s use. In addition, placement of such weights within the shaft can move the club head""s center of gravity to an undesired location. Further, if the need ever arises to replace the club""s shaft, the weight will necessarily be removed and an equivalent weight might not be installed in its place.
Yet another common form for the added weight component has been a plurality of metallic weights carried within correspondingly sized cavities formed in a housing that is secured, e.g., by screws, to a portion of the golf club head, typically the sole. Although generally effective in providing the club head with the desired weight, the process of assembling such weight components is considered to require excessive manufacturing effort and cost. Also, the housing and/or weight components sometimes can loosen during the club""s use.
It should therefore be appreciated that there is a need for an improved golf club head, and method for making it, in which the head""s weight can be tailored to a precisely selected value, without adversely affecting important parameters such as the club head""s coefficient of restitution or center of gravity, without being susceptible to loosening when the club is used or when the club""s shaft is removed or replaced, and without requiring excessive time and effort during manufacture. The present invention fulfills this need and provides further related advantages.
The present invention resides in an improved golf club head, and in a method for making it, in which the weight of the head is tailored to a precisely selected value without adversely affecting club head parameters such as coefficient of restitution or center of gravity, without being susceptible to loosening when the club head is used or when the associated shaft is removed or replaced, and without requiring excessive time and effort during manufacture. The golf club head includes a hollow main body having a sole, a crown, a heel, a toe, a ball-striking face, and a rear wall, with the heel defining a hosel for receiving the lower end of a shaft, and the rear wall defining a rear wall cavity for receiving a special weight cartridge. The hollow main body defines a central axis along which the head is intended to move when being used to strike a golf ball. The weight cartridge includes a polymeric housing having one or more elongated cavities for conformably receiving one or more weights. The rear wall cavity is substantially aligned with the central axis and is sized and configured to conformably and slidably receive the polymeric housing, along an axis substantially aligned with the central axis. The weight cartridge is secured within the rear wall cavity, in an installation position, without the need for a screw attachment.
The weight cartridge is selected from a plurality of weight cartridges, all having substantially the same size and shape, but each having a different weight. The particular weight cartridge is selected so that its weight will provide the golf club head with the desired total weight.
In its preferred form, the rear wall cavity has a substantially rectangular cross-section in planes perpendicular to the central axis, and spaced above the sole of the head. The weight cartridge is retained in its installation position within the rear wall cavity by a snap fit, and/or by an interference fit, and/or by a bonding material such as double-sided tape and/or epoxy. When a snap fit attachment is being used, the housing and cavity, together, include a cooperating ridge and groove structure.
The one or more weights preferably comprise material selected from the group consisting of polymers, aluminum, steel and tungsten. The cavities defined by the polymeric housing preferably are at least three in number, each cavity having an elongated, substantially cylindrical shape, and the plurality of weights each have a substantially cylindrical shape sized to fit snugly within these cavities. The plurality of weight cartridges have weights that range from about 3 g to about 16 g, which represents about 1.5% to about 8% of the golf club head""s total weight.
In yet further more detailed features of the invention, the polymeric housing has a top wall, a bottom wall, a front wall, left and right side walls, and a rear wall, and substantially only the rear wall of the housing is visible when the housing is located in its installation position. The cavities defined by the polymeric housing open into a wall of the housing other than the rear wall, such that the weights are prevented from exiting the housing when the housing is located in its installation position. Preferably, the cavities open into the front wall of the housing, and they are oriented with their longitudinal axes substantially parallel with each other and with the club head""s central axis.
Other features and advantages of the invention should become apparent from the following description of the preferred embodiment, taken in conjunction with the accompanying drawings, which illustrate, by way of example, the principles of the invention.


A weighted article for providing deep pressure therapy includes a plurality of patchwork pieces including a plurality of layers. At least some of the patchwork pieces include a filler of weighted material contained between at least two of the plurality of layers. The plurality of patchwork pieces are fastened together at edges.

Deep pressure therapy has been found to be useful in the treatment of a variety of disorders where anxiety is an issue. Such disorders include developmental disorders including Autistic Spectrum Disorder, Attention-Deficit/Hyperactivity Disorder (ADHD), Pervasive Developmental Disorder Not Otherwise Specified (PDD-NOS), and Alzheimer's. Deep pressure therapy is also useful in the treatment of anxiety, insomnia, and other common problems.
Deep pressure therapy is a term sometimes used to refer to the application of pressure to a person. The therapy generates sensations in the body, such as those arising from hugging, cuddling, squeezing, stroking, or holding. One type of deep pressure therapy involves the use of a weighted blanket containing a weighted material distributed within the blanket. The blanket is placed over a part of the body and applies general pressure to that part of the body.


A method of compressing digital data includes the steps of (i) reading digital data as a series of binary coded words representing a context and a code word to be compressed, (ii) calculating distribution output data from the input data and assigning variable length code words to the result; and (iii) periodically recalculating the code words in accordance with a predetermined schedule, in order to continuously update the code words and their lengths.

The video to be compressed can be considered as consisting of a number of frames (at least 1), each made up of individual picture elements, or pixels. Each pixel can be represented by three components, usually either RGB (red, green and blue) or YUV (luminance and two chrominance values). These components can be any number of bits each, but eight bits of each is usually considered sufficient.
The human eye is more sensitive to the location of edges in the Y values of pixels than the location of edges in U and V. For this reason, the preferred implementation here uses the YUV representation for pixels.
The image size can vary, with more pixels giving higher resolution and higher quality, but at the cost of higher data rate. Where the source video is in PAL format, the image fields have 288 lines with 25 frames per second. Square pixels give a source image size of 384×288 pixels. The preferred implementation has a resolution of 376×280 pixels using the central pixels of a 384×288 pixel image, in order to remove edge pixels which are prone to noise and which are not normally displayed on a TV set.
The images available to the computer generally contain noise so that the values of the image components fluctuate. These source images are filtered as the first stage of the compression process. The filtering reduces the data rate and improves the image quality of the compressed video.
A further stage analyses the contents of the video frame-by-frame and determines which of a number of possible types pixel should be allocated to. These broadly correspond to pixels in high contrast areas and pixels in low contrast areas.
The pixels are hard to compress individually, but there are high correlations between each pixel and its near neighbours. To aid compression, the image is split into one of a number of different types of components. The simpler parts of the image split into rectangular components, called "super-blocks" in this application, which can be thought of as single entities with their own structure. These blocks can be any size, but in the preferred implementation described below, the super-blocks are all the same size and are 8×8 pixel squares. More structurally complex parts of the image where the connection between pixels further apart is less obvious are split up into smaller rectangular components, called "mini-blocks" in application.
It is apparent that if each super-block is compressed separately, the errors resulting from the compression process can combine across edges between super-blocks thus illustrating the block-like nature of the compression by highlighting edges between blocks, which is undesirable. To avoid this problem, the mini-blocks are tokenised with an accurate representation and these are compressed in a loss free way.
Each super-block or mini-block is encoded as containing YUV information of its constituent pixels.
This U and V information is stored at lower spatial resolution than the Y information, in one implementation with only one value of each of U and V for every mini-block. The super-blocks are split into regions. The colour of each one of these regions is represented by one UV pair.
Real Time Filtering
The aim is to remove noise from the input video, as noise is by definition hard to compress. The filtering mechanism takes frames one at a time. It compares the current frame with the previous filtered frame on a pixel-by-pixel basis. The value for the previous pixel is used unless there is a significant difference. This can occur in a variety of ways. In one, the value of the pixel in the latest frame is a long way from the value in the previous filtered frame. In another, the difference is smaller, but consistently in the same direction. In another, the difference is even smaller, but cumulatively, over a period of time, has tended to be in the same direction. In these the first two cases, the pixel value is updated to the new value. In the third case, the filtered pixel value is updated by a small amount in the direction of the captured video. The allowable error near a spatial edge is increased depending on the local contrast to cut out the effects of spatial jitter on the input video.
Real Time Motion Estimation
The video frames are filtered into "Noah regions". Thus the pixels near to edges are all labelled. In a typical scene, only between 2% and 20% of the pixels in the image turn out to have the edge labelling. There are three types of motion estimation used. In the first, whole frame pan detection using integer number of pixels is implemented. These motions can be implemented efficiently over the whole image on playback as pixels can be copied to new locations and no blurring is needed. This uses the edge areas from the Noah regions only as the edges contain the information needed for an accurate motion search. The second is sub-pixel motion removal over the whole image. This uses the edge areas from the Noah regions only as the edges contain the information needed for an accurate motion search. The edge pixels in the image, estimated by example from the Noah filtering stage, are matched with copies of themselves with translations of up to e.g., 2 pixels, but accurate to e.g., 1/64 pixel (using a blurring function to smooth the error function) and small rotations. The best match is calculated by a directed search starting at a large scale and increasing the resolution until the required sub-pixel accuracy is attained. This transformation is then applied in reverse to the new image frame and filtering continues as before. These changes are typically ignored on playback. The effect is to remove artifacts caused by camera shake, significantly reducing datarate and giving an increase in image quality. The third for examines local areas of the image. Where a significant proportion of the pixels are updated, for example on an 8×8 pixel block, either motion vectors are tested in this area with patches for the now smaller-temporal deltas, or a simplified super-block representation is used giving either 1 or 2 YUVs per block, and patches are made to this.
Real Time Fade Representation
The encoding is principally achieved by representing the differences between consecutive compressed frames. In some cases, the changes in brightness are spatially correlated. In this case, the image is split into blocks or regions, and codewords are used to specify a change over the entire region, with differences with these new values rather than differences to the previous frame itself being used.
Segment Noah Regions—Find Edges
A typical image consists of areas with low contrast and areas of high contrast, or edges. The segmentation stage described here analyses the image and decides whether any pixel is near an edge or not. It does this by looking at the variance in a small area containing the pixel. For speed, in the current implementation, this involves looking at a 3×3 square of pixels with the current pixel at the centre, although future implementations on faster machines can be expected to look at a larger area. The pixels which are not near edges are compressed using an efficient but simple representation which includes multiple pixels—for example 2×2 blocks or 8×8 blocks, which are interpolated on playback. The remaining pixels near edges are represented as either e.g., 8×8 blocks with a number of YUV areas (typically 2 or 3) if the edge is simply the boundary between two or more large regions which just happen to meet here, or as 2×2 blocks with 1Y and one UV per block in the case that the above simple model does not apply e.g., when there is too much detail in the area because the objects in this area are too small.
Miniblockify
The image is made up of regions, which are created from the Noah regions. The relatively smooth areas are represented by spatially relatively sparse YUV values, with the more detailed regions such as the Noah edges being represented by 2×2 blocks which are either uniform YUV, or consist of a UV for the block and maximum Y and a minimum Y, with a codeword to specify which of the pixels in the block should be the maximum Y value and which should be the minimum. To further reduce the datarate, the Y pairs in the non-uniform blocks are restricted to a subset of all possible Y pairs which is more sparse when the Y values are far apart.
Transitions with Variable Lengths Codewords
Compressing video consists in part of predicting what the next frame will as accurately as possible from the available data, or context. Then the (small) unpredictable element is what is sent in the bitstream, and this is combined with the prediction to give the result. The transition methods described here are designed to facilitate this process. On compression, the available context and codeword to compress are passed to the system. This then adds this information to its current distribution (which it is found performs well when it starts with no prejudice as the likely relationship between the context and the output codeword). The distribution output data for this context is calculated and variable length codewords assigned to the outcomes which have arisen. These variable length codewords are not calculated each time the system is queried as the cost/reward ratio makes it unviable, particularly as the codewords have to be recalculated on the player at the corresponding times they are calculated on the compressor. Instead, the codewords are recalculated from time to time. For example, every new frame, or every time the number of codewords has doubled. Recalculation every time an output word is entered for the first time is too costly in many cases, but this is aided by not using all the codeword space every time the codewords are recalculated. Codeword space at the long end is left available, and when new codewords are needed then next one is taken. As these codewords have never occurred up to this point, they are assumed to be rare, and so giving them long codewords is not a significant hindrance. When the codeword space is all used up, the codewords are recalculated. The minimum datarate for Huffman codewords is a very flat and wide minimum, so using the distribution from the codewords which have occurred so far is a good approximation to the optimal. Recalculating the codewords has to happen quickly in a real time system. The codewords are kept sorted in order of frequency, with the most frequent codewords first. The sorting is a mixture of bin sort using linked lists which is O(n) for the rare codewords which change order quite a lot, and bubble sort for the common codewords which by their nature to not change order by very much each time a new codeword is added. The codewords are calculated by keeping a record of the unused codeword space, and the proportion of the total remaining codewords the next data to encode takes. The shorted codeword when the new codeword does not exceed its correct proportion of the available codeword space is used. There is are further constraints—in order to keep the codes as prefix codes and to allow spare space for new codewords, codewords never get shorter in length, and each codeword takes up an integer power of two of the total codeword space. This method creates the new codewords into a lookup table for quick encoding in O(n) where n is the number of sorted codewords.
Memory Management
To facilitate Java playback, all the memory used is allocated in one block at the start. As garbage collection algorithms on Java virtual machines are unpredictable, and many stop the system for periods which are long in comparison to the length of a video frame, the invention may use its own memory management system. This involves allocating enough memory for e.g., 2 destination codewords for each source codeword when it is first encountered. New transitions are added as and when they occur, and when the available space for them overflows, the old memory is ignored, and new memory of twice the size is allocated. Although up to half the memory may end up unused, the many rare transitions take almost no memory, and the system scales very well and makes no assumption about the distribution of transitions.
Give Compressed Codeword for this Uncompressed Codeword
Every time a codeword occurs in a transition for the second or subsequent time, its frequency is updated and it is re-sorted. When it occurs for the first time in this transition however, it must be defined. As many codewords occur multiple times in different transitions, the destination value is encoded as a variable length codeword each time it is used for the first time, and this variable length codeword is what is sent in the bitstream, preceded by a "new local codeword" header codeword. Similarly, when it occurs for the first time ever, it is encoded raw preceded by a "new global codeword" header codeword. These header codewords themselves are variable length and recalculated regularly, so they start off short as most codewords are new when a new environment is encountered, and they gradually lengthen as the transitions and concepts being encoded have been encountered before.
Video Compression (Cuts)
Cuts are compressed using spatial context from the same frame.
Cuts, RLE uniform shape, else assume independent and context=CUT_CW.
Cuts→editable, so needs efficient. First approximation at lower resolution e.g., 8×8.
Cuts—predict difference in mini-block codewords from previous one and uniform flag for current one.
Video Compression (Deltas)
The deltas can use temporal and spatial context.
Deltas shape—predict shape from uniformness of four neighbours and old shape.
Deltas—predict mini-block codeword differences from uniformness of this mini-block and old mini-block in time.
Datarate Reductions
Various simple but effective datarate reduction methods are employed. Noise in the input signal can lead to isolated small changes over the image, whose loss would not be noticed. Isolated changed mini-blocks are generally left out from the bitstream, though if the mini-block is sufficiently different they can still be updated. In addition, small changes in colour in high colour areas are generally ignored as these are almost always caused by noise.
Multi-level Gap Masks: 4×4, 16×16, 64×64
The bulk of the images are represented mbs and gaps between them. The gaps are spatially and temporally correlated. The spatial correlation is catered for by dividing the image into 4×4 blocks of mbs, representing 64 pixels each, with one bit per mini-block representing whether the mbs has changed on this frame. These 4×4 blocks are grouped into 4×4 blocks of these, with a set bit if any of the mbs it represents have changed. Similarly, these are grouped into 4×4 blocks, representing 128×128 pixels, which a set bit if any of the pixels has changed in the compressed representation. It turns out that trying to predict 16 bits at a time is too ambitious as the system does not have time to learn the correct distributions in a video of typical length. Predicting the masks 4×2 pixels at a time works well. The context for this is the corresponding gap masks from the two previous frames. The transition infrastructure above then gives efficient codewords for the gaps at various scales.
Multiple Datarates at Once
One of the features of internet or intranet video distribution is that the audience can have a wide range of receiving and decoding equipment. In particular the connection speed may vary widely. In a system such as this designed for transmission across the internet, it helps to support multiple datarates. So the compression filters the image once, then resamples it to the appropriate sizes involving for example cropping so that averaging pixels to make the final image the correct size involves averaging pixels in rectangular blocks of fixed size. There is a sophisticated datarate targeting system which skips frames independently for each output bitstream. The compression is sufficiently fast on a typical modern PC of this time to create modem or midband videos with multiple target datarates. The video is split into files for easy access, and these files may typically be 10 seconds long, and may start with a key frame. The player can detect whether its pre-load is ahead or behind target and load the next chunk at either lower or higher datarate to make use of the available bandwidth. This is particularly important if the serving is from a limited system where multiple simultaneous viewers may wish to access the video at the same time, so the limit to transmission speed is caused by the server rather than the receiver. The small files will cache well on a typical internet setup, reducing server load if viewers are watching the video from the same ISP, office, or even the same computer at different times.
Key Frames
The video may be split into a number of files to allow easy access to parts of the video which are not the beginning. In these case, the files may start with a key frame. A key frame contains all information required to start decompressing the bitstream from this point, including a cut-style video frame and information about the status of the transition tables, such as starting with completely blank tables.
Digital Rights Management
DRM is an increasingly important component of a video solution, particularly now content is so readily accessible of the internet. Data typically included in DRM may an expiry data for the video, a restricted set of URLs the video can be played from. Once the compressor itself is sold, the same video may be compressed twice with different DRM data in an attempt to crack the DRM by looking at the difference between the two files. The compression described here is designed to allow small changes to the initial state of the transition or global compression tables to effectively randomise the bitstream. By randomizing a few bits each time a video is compressed, the entire bitstream is randomized each time the video is compressed, making it much harder to detect differences in compressed data caused by changes to the information encoded in DRM.
Miscellaneous
The Y values for each pixel within a single super-block can also be approximated. In many cases, there is only one or part of one object in a super-block. In these cases, a single Y value is often sufficient to approximate the entire super-block's pixel Y values, particularly when the context of neighbouring super-blocks is used to help reconstruct the image on decompression.
In many further cases, there are only two or parts of two objects in a super-block. In these cases, a pair of Y values is often sufficient to approximate the entire super-block's Y values, particularly when the context of the neighbouring super-blocks is used to help reconstruct the image on decompression. In the cases where there are two Y values, a mask is used to show which of the two Y values is to be used for each pixel when reconstructing the original super-block. These masks can be compressed in a variety of ways, depending on their content, as it turns out that the distribution of masks is very skewed. In addition, masks often change by small amounts between frames, allowing the differences between masks on different frames to be compressed efficiently.
Improvements to image quality can be obtained by allowing masks with more than two Y values, although this increases the amount of information needed to specify which Y value to use.
Although the invention has been described with particular reference to video data, it will be appreciated that it could also be applied to other types of data such as audio data.


The conditioning performance of small particle size emulsified silicone in a surfactant-based shampoo composition can be significantly boosted by the inclusion in the shampoo composition of an amino functionalised silicone. Accordingly, the invention provides an aqueous shampoo composition comprising, in addition to water:

This invention relates to shampoo compositions, and more particularly to shampoo compositions containing emulsified particles of silicone, which compositions condition the hair leaving it softer and more manageable.
The use of silicones as conditioning agents in cosmetic formulations is well known and widely documented in the patent literature. Generally, dispersed droplets of the silicone oil are suspended in the composition, which is then applied to the hair to deposit the silicone material on the hair shaft.
A typical method of silicone shampoo manufacture is disclosed in WO 92/10162. Essentially, the silicone material is emulsified directly into the shampoo by an in situ hot process, in which the complete shampoo mixture incorporating the silicone is mixed thoroughly at elevated temperature, pumped through a high shear mill and then cooled. The silicone can be dispersed in a first process stage with anionic surfactant and fatty alcohol to form a premix. The premix is then mixed with the remaining materials of the shampoo, pumped through a high shear mill, and cooled to obtain the final composition.
A disadvantage associated with an in situ hot process such as is described in WO 92/10162 is that factory handling of viscous silicone oil is difficult in the context of a full shampoo manufacturing operation.
A further disadvantage is that special equipment is normally needed to control silicone particle size during manufacture. GB 2 170 216 A discloses a similar process, in which the full shampoo composition incorporating insoluble, non-volatile silicone is sheared with a high shear mixer until the silicone particles are on average less than 2 microns in diameter. The particle size distribution is then said to be from about 2 to about xe2x88x9255 microns.
In order to solve the above mentioned problems with in situ hot processing of silicone, the alternative of incorporating the silicone as a preformed aqueous emulsion has been proposed. Such a method has the consequences that the silicone is incorporated with a predeterminable, controllable particle size distribution. The silicone is insoluble and remains emulsified in the fully formulated shampoo composition, and thus the step of high shear processing of the silicone within the fully formulated shampoo composition is not required. This also makes manufacture of the compositions easier.
A typical method for incorporating insoluble, non-volatile silicone materials into a conditioning shampoo is disclosed in U.S. Pat. No. 5,085,857 in which such materials are incorporated in the shampoo composition as a pre-formed aqueous emulsion of average particle size less than 2 microns. All the ingredients are mixed in a simple hot or cold process in which the average particle size of the silicone material in the emulsion remains the same in the final shampoo composition. Preferably, this size is from 0.01 to 1 micron, e.g. 0.4 micron.
EP 0 529 883 A1 discloses hair shampoo compositions made by an equivalent method and comprising microemulsified particles of silicone having a particle size of 0.15 microns or less, e.g., 0.036 microns. Reducing the silicone particle size still further in this way is said to improve stability, optical properties and conditioning performance.
A problem encountered with these small particle size silicone formulations is that the conditioning performance may be insufficient for many people, particularly in regions such as Japan and South East Asia where consumers desire a high level of conditioning and a xe2x80x9cweightyxe2x80x9d feel to their hair.
We have now found that the conditioning performance of small particle size emulsified silicone in a surfactant-based shampoo composition can be significantly boosted by the inclusion in the shampoo composition of an amino functionalised silicone.
U.S. Pat. No. 5,198,209 (Amway Corp) and L""Oreal EP 0 811 371 disclose conditioning shampoos with cleansing surfactant and a combination of dimethicone and trimethylsilylamodimethicone. The exemplified compositions use dimethicone fluid such as DC200 (60,000 cst). The dimethicone fluid is added directly to the shampoo as neat silicone oil of unspecified silicone particle size.
The invention provides an aqueous shampoo composition comprising, in addition to water:
i) at least one surfactant chosen from anionic, nonionic, zwitterionic or amphoteric surfactants or mixtures thereof;
ii) an amino functionalised silicone; and
iii) emulsified particles of an insoluble, non-amino functionalised silicone, in which the average silicone particle size of the emulsified non-amino functional silicone in the shampoo composition is less than 2 microns.
Surfactant
The composition according to the invention comprises a surfactant chosen from anionic, nonionic, zwitterionic or amphoteric surfactants or mixtures thereof.
Suitable anionic surfactants include the alkyl sulphates, alkyl ether sulphates, alkaryl sulphonates, alkanoyl isethionates, alkyl succinates, alkyl sulphosuccinates, N-alkoyl sarcosinates, alkyl phosphates, alkyl ether phosphates, alkyl ether carboxylates, and alpha-olefin sulphonates, especially their sodium, magnesium ammonium and mono-, di- and triethanolamine salts. The alkyl and acyl groups generally contain from 8 to 18 carbon atoms and may be unsaturated. The alkyl ether sulphates, alkyl ether phosphates and alkyl ether carboxylates may contain from one to 10 ethylene oxide or propylene oxide units per molecule, and preferably contain 2 to 3 ethylene oxide units per molecule.
Examples of suitable anionic surfactants include sodium oleyl succinate, ammonium lauryl sulphosuccinate, ammonium lauryl sulphate, sodium dodecylbenzene sulphonate, triethanolamine dodecylbenzene sulphonate, sodium cocoyl isethionate, sodium lauroyl isethionate and sodium N-lauryl sarcosinate. The most preferred anionic surfactants are sodium lauryl sulphate, triethanolamine lauryl sulphate, triethanolamine monolauryl phosphate, sodium lauryl ether sulphate 1EO, 2EO and 3EO, ammonium lauryl sulphate and ammonium lauryl ether sulphate 1EO, 2EO and 3EO.
Nonionic surfactants suitable for use in compositions of the invention may include condensation products of aliphatic (C8-C18) primary or secondary linear or branched chain alcohols or phenols with alkylene oxides, usually ethylene oxide and generally having from 6 to 30 ethylene oxide groups. Other suitable nonionics include mono- or di-alkyl alkanolamides. Example include coco mono- or di-ethanolamide and coco mono-isopropanolamide.
Amphoteric and zwitterionic surfactants suitable for use in compositions of the invention may include alkyl amine oxides, alkyl betaines, alkyl amidopropyl betaines, alkyl sulphobetaines (sultaines), alkyl glycinates, alkyl carboxyglycinates, alkyl amphopropionates, alkylamphoglycinates alkyl amidopropyl hydroxysultaines, acyl taurates and acyl glutamates, wherein the alkyl and acyl groups have from 8 to 19 carbon atoms. Examples include lauryl amine oxide, cocodimethyl sulphopropyl betaine and preferably lauryl betaine, cocamidopropyl betaine and sodium cocamphopropionate.
Generally, the surfactants are present in shampoo compositions of the invention in an amount of from 0.1 to 50%, preferably from 5 to 30%, more preferably from 10% to 25% by weight.
Amino Functionalised Silicone
By xe2x80x9camino functionalised siliconexe2x80x9d is meant a silicone containing at least one primary, secondary or tertiary amine group, or a quaternary ammonium group.
Examples Include
(i) polysiloxanes having the CTFA designation xe2x80x9camodimethiconexe2x80x9d, and the general formula:
HOxe2x80x94[Si(CH3)2xe2x80x94Oxe2x80x94]xxe2x80x94[Si(OH)(CH2CH2CH2xe2x80x94NHxe2x80x94CH2CH2NH2)xe2x80x94Oxe2x80x94]yxe2x80x94H
in which x and y are numbers depending on the molecular weight of the polymer, generally such that the molecular weight is between about 5,000 and 500,000.
(ii) polysiloxanes having the general formula:
Rxe2x80x2aG3xe2x88x92axe2x80x94Si(OSiG2)nxe2x80x94(OSiGbRxe2x80x22xe2x88x92b)mxe2x80x94Oxe2x80x94SiG3xe2x88x92axe2x80x94Rxe2x80x2a
in which:
G is selected from H, phenyl, OH or C1-8 alkyl, e.g. methyl;
a is 0 or an integer from 1 to 3, preferably 0;
b is 0 or 1, preferably 1;
m and n are numbers such that (m+n) can range from 1 to 2000, preferably from 50 to 150;
m is a number from 1 to 2000, preferably from 1 to 10;
n is a number from 0 to 1999, preferably from 49 to 149, and
Rxe2x80x2 is a monovalent radical of formula xe2x80x94CqH2qL in which q is a number from 2 to 8 and L is an aminofunctional group selected from the following:
xe2x80x94NRxe2x80x3xe2x80x94CH2xe2x80x94CH2xe2x80x94N (Rxe2x80x3)2
xe2x80x94N(Rxe2x80x3)2
xe2x80x94N+(Rxe2x80x3)3Axe2x88x92
xe2x80x94N+H(Rxe2x80x3)2Axe2x88x92
xe2x80x94N+H2(Rxe2x80x3)Axe2x88x92
xe2x80x94N(Rxe2x80x3)xe2x80x94CH2xe2x80x94CH2xe2x80x94N+H2(Rxe2x80x3)Axe2x88x92
in which Rxe2x80x2 is selected from H, phenyl, benzyl, or a saturated monovalent hydrocarbon radical, e.g. C1-20 alkyl, and
A is a halide ion, e.g. chloride or bromide.
Suitable amino functionalised silicones corresponding to the above formula include those polysiloxanes termed xe2x80x9ctrimethylsilylamodimethiconexe2x80x9d as depicted below, and which are sufficiently water insoluble so as to be useful in compositions of the invention:
Si(CH3)3xe2x80x94Oxe2x80x94[Si(CH3)2xe2x80x94Oxe2x80x94]xxe2x80x94[Si(CH3)(Rxe2x80x94NHxe2x80x94CH2CH2NH2)xe2x80x94Oxe2x80x94]yxe2x80x94Si(CH3)3
wherein x+y is a number from about 50 to about 500, and wherein R is an alkylene group having from 2 to 5 carbon atoms. Preferably, the number x+y is in the range of from about 100 to about 300.
(iii) quaternary silicone polymers having the general formula:
{(R1)(R2)(R3)N+CH2CH(OH)CH2O(CH2)3[Si(R4)(R5)xe2x80x94Oxe2x80x94]nxe2x80x94Si(R6)(R7)xe2x80x94(CH2)3xe2x80x94Oxe2x80x94CH2CH(OH)CH2N+(R8)(R9)(R10)}(Xxe2x88x92)2
wherein
R1 and R10 may be the same or different and may be independently selected from H, saturated or unsaturated long or short chain alk(en)yl, branched chain alk(en)yl and C5-C8 cyclic ring systems;
R2 thru"" R9 may be the same or different and may be independently selected from H, straight or branched chain lower alk(en)yl, and C5-C8 cyclic ring systems;
n is a number within the range of about 60 to about 120, preferably about 80, and
Xxe2x88x92 is preferably acetate, but may instead be for example halide, organic carboxylate, organic sulphonate or the like.
Suitable quaternary silicone polymers of this class are described in EP-A-0 530 974.
Amino functional silicones suitable for use in the invention will typically have a mole % amine functionality in the range of from about 0.1 to about 8.0 mole %, preferably from about 0.1 to about 5.0 mole %, most preferably from about 0.1 to about 2.0 mole %. In general the amine concentration should not exceed about 8.0 mole % since we have found that too high an amine concentration can be detrimental to total silicone deposition and therefore conditioning performance.
The viscosity of the amino functional silicone is not particularly critical and can suitably range from about 100 to about 500,000 cst.
Specific examples of amino functional silicones suitable for use in the invention are the aminosilicone oils DC2-8220, DC2-81606, DC2-8466, and DC2-8950-114 (all ex Dow Corning), and GE 1149-75, (ex General Electric Silicones).
Also suitable are emulsions of amino functional silicone oils with non ionic and/or cationic surfactant.
Suitably such pre-formed emulsions will have an average amino functional silicone particle size in the shampoo composition of less than 30, preferably less than 20, more preferably less than 10 microns. We have found that reducing the particle size generally improves conditioning performance. Most preferably the average amino functional silicone particle size is less than 2 microns, ideally it ranges from 0.01 to 1 micron. Silicone emulsions having an average silicone particle size of xe2x89xa60.15 microns are generally termed microemulsions.
Particle size may be measured by means of a laser light scattering technique, using a 2600D Particle Sizer from Malvern Instruments.
Pre-formed emulsions of amino functionalised silicone are available from suppliers of silicone oils such as Dow Corning and General Electric. Specific examples include DC929 Cationic Emulsion, DC939 Cationic Emulsion, DC949 Cationic Emulsion, and the non-ionic emulsions DC2-7224, DC2-8467 and DC2-8154 (all ex Dow Corning).
An example of a quaternary silicone polymer useful in the present invention is the material K3474, ex Goldschmidt.
Emulsified, Non-amino Functionalised Silicone
The shampoo composition of the invention comprises a non-amino functionalised silicone. The silicone is insoluble in the aqueous matrix of the shampoo composition and so is present in an emulsified form, with the silicone present as dispersed particles.
The average silicone particle size of the emulsified non-amino functional silicone in the shampoo composition is less than 2 microns. Ideally it ranges from 0.01 to 1 micron. We have found that reducing the particle size in this way improves the overall conditioning performance from the shampoo composition. Particle size may be measured by means of a laser light scattering technique, using a 2600D Particle Sizer from Malvern Instruments.
Suitable silicones include polydiorganosiloxanes, in particular polydimethylsiloxanes which have the CTFA designation dimethicone. Also suitable for use in shampoo compositions of the invention are polydimethyl siloxanes having hydroxyl end groups, which have the CTFA designation dimethiconol. Also suitable for use in shampoos of the invention are silicone gums having a slight degree of cross-linking, as are described for example in WO 96/31188. These materials can impart body, volume and stylability to hair, as well as good wet and dry conditioning.
Various methods of making emulsions of particles of silicones for use in the invention are available and are well known and documented in the art. For example, emulsions may be prepared by high shear mechanical mixing of the silicone and water, or by emulsifying the silicone with water and an emulsifier (mixing the silicone into a heated solution of the emulsifier for instance), or by a combination of mechanical and chemical emulsification. A further suitable technique for preparation of emulsions of particles of silicones is emulsion polymerisation. Emulsion polymerised silicones as such are described in U.S. Pat. No. 2,891,820 (Hyde), U.S. Pat. No. 3,294,725 (Findlay) and U.S. Pat. No. 3,360,491 (Axon).
Suitable silicone emulsions for use in the invention are commercially available in a pre-emulsified form. This is particularly preferred since the pre-formed emulsion can be incorporated into the shampoo composition by simple mixing. Pre-formed emulsions are available from suppliers of silicone oils such as Dow Corning, General Electric, Union Carbide, Wacker Chemie, Shin Etsu, Toshiba, Toyo Beauty Co, and Toray Silicone Co.
The viscosity of the silicone itself (not the emulsion or the final shampoo composition) is typically at least 10,000 cst. In general we have found that conditioning performance increases with increased viscosity. Accordingly, the viscosity of the silicone itself is preferably at least 60,000 cst, most preferably at least 500,000 cst, ideally at least 1,000,000 cst. Preferably the viscosity does not exceed 109 cst for ease of formulation. Viscosity can be measured by means of a glass capillary viscometer as set out further in Dow Corning Corporate Test Method CTM004 Jul. 20 1970.
Examples of suitable pre-formed emulsions include emulsions DC2-1766, DC2-1784, and microemulsions DC2-1865 and DC2-1870, all available from Dow Corning. These are all emulsions/microemulsions of dimethiconol. DC2-1766 and DC2-1784 each have an average silicone particle size in the emulsion of less than 2 microns. DC2-1865 and DC2-1870 each have an average silicone particle size in the microemulsion of less than 0.15 microns. Cross-linked silicone gums are also available in a pre-emulsified form, which is advantageous for ease of formulation. A preferred example is the material available from Dow Corning as DC X2-1787, which is an emulsion of cross-linked dimethiconol gum having an average silicone particle size in the emulsion of 0.5 microns. A further preferred example is the material available from Dow Corning as DC X2-1391, which is a microemulsion of cross-linked dimethiconol gum having an average silicone particle size in the microemulsion of 0.045 microns.
Silicone Ratios
We have found that the conditioning performance of small particle size emulsified silicone in a surfactant-based shampoo composition can be significantly boosted by the presence of an amino functionalised silicone.
The weight ratio of amino functionalised silicone to non-amino functionalised silicone is generally 1:2 or less. Suitably, the ratio of amino functionalised silicone to non-amino functionalised silicone ranges from 1:2 to 1:20, preferably 1:3 to 1:20, more preferably 1:3 to 1:8, optimally around 1:4.
Silicone Levels
The total amount of silicone (amino functional and non-amino functional) incorporated into the shampoo compositions of the invention depends on the level of conditioning desired and the material used. A preferred amount is from 0.01 to about 10% by weight of the total composition although these limits are not absolute. The lower limit is determined by the minimum level to achieve conditioning and the upper limit by the maximum level to avoid making the hair and/or skin unacceptably greasy.
We have found that a total amount of silicone of from 0.3 to 5%, preferably 0.5 to 3%, by weight of the total composition is a suitable level.
Cationic Deposition Polymer
A cationic deposition polymer is a preferred ingredient in shampoo compositions of the invention, for enhancing conditioning performance of the shampoo. By xe2x80x9cdeposition polymerxe2x80x9d is meant an agent which enhances deposition of the silicone component from the shampoo composition onto the intended site during use, i.e. the hair and/or the scalp.
The deposition polymer may be a homopolymer or be formed from two or more types of monomers. The molecular weight of the polymer will generally be between 5 000 and 10 000 000, typically at least 10 000 and preferably in the range 100 000 to about 2 000 000. The polymers will have cationic nitrogen containing groups such as quaternary ammonium or protonated amino groups, or a mixture thereof.
The cationic nitrogen-containing group will generally be present as a substituent on a fraction of the total monomer units of the deposition polymer. Thus when the polymer is not a homopolymer it can contain spacer non-cationic monomer units. Such polymers are described in the CTFA Cosmetic Ingredient Directory, 3rd edition. The ratio of the cationic to non-cationic monomer units is selected to give a polymer having a cationic charge density in the required range. Suitable cationic deposition polymers include, for example, copolymers of vinyl monomers having cationic amine or quaternary ammonium functionalities with water soluble spacer monomers such as (meth)acrylamide, alkyl and dialkyl (meth)acrylamides, alkyl (meth)acrylate, vinyl caprolactone and vinyl pyrrolidine. The alkyl and dialkyl substituted monomers preferably have C1-C7 alkyl groups, more preferably C1-C3 alkyl groups. Other suitable spacers include vinyl esters, vinyl alcohol, maleic anhydride, propylene glycol and ethylene glycol.
The cationic amines can be primary, secondary or tertiary amines, depending upon the particular species and the pH of the composition. In general secondary and tertiary amines, especially tertiary, are preferred.
Amine substituted vinyl monomers and amines can be polymerized in the amine form and then converted to ammonium by quaternization.
The cationic deposition polymers can comprise mixtures of monomer units derived from amine- and/or quaternary ammonium-substituted monomer and/or compatible spacer monomers.
Suitable cationic deposition polymers include, for example:
copolymers of 1-vinyl-2-pyrrolidine and 1-vinyl-3-methyl-imidazolium salt (e.g. chloride salt), referred to in the industry by the Cosmetic, Toiletry, and Fragrance Association, (CTFA) as Polyquaternium-16. This material is commercially available from BASF Wyandotte Corp. (Parsippany, N.J., USA) under the LUVIQUAT tradename (e.g. LUVIQUAT FC 370);
copolymers of 1-vinyl-2-pyrrolidine and dimethylaminoethyl methacrylate, referred to in the industry (CTFA) as Polyquaternium-11. This material is available commercially from Gaf Corporation (Wayne, N.J., USA) under the GAFQUAT tradename (e.g., GAFQUAT 755N);
cationic diallyl quaternary ammonium-containing polymers including, for example, dimethyldiallyammonium chloride homopolymer and copolymers of acrylamide and dimethyldiallylammonium chloride, referred to in the industry (CTFA) as Polyquaternium 6 and Polyquaternium 7, respectively;
mineral acid salts of amino-alkyl esters of homo- and co-polymers of unsaturated carboxylic acids having from 3 to 5 carbon atoms, (as described in U.S. Pat. No. 4,009,256);
cationic polyacrylamides(as described in WO95/22311). Other cationic deposition polymers that can be used include cationic polysaccharide polymers, such as cationic cellulose derivatives, cationic starch derivatives, and cationic guar gum gerivatives.
Cationic polysaccharide polymers suitable for use in compositions of the invention include those of the formula:
xe2x80x94Axe2x80x94Oxe2x80x94[Rxe2x80x94N+(R1)(R2)(R3)Xxe2x88x92],
wherein: A is an anhydroglucose residual group, such as a starch or cellulose anhydroglucose residual. R is an alkylene, oxyalkylene, polyoxyalkylene, or hydroxyalkylene group, or combination thereof. R1, R2 and R3 independently represent alkyl, aryl, alkylaryl, arylalkyl, alkoxyalkyl, or alkoxyaryl groups, each group containing up to about 18 carbon atoms. The total number of carbon atoms for each cationic moiety (i.e., the sum of carbon atoms in R1, R2 and R3) is preferably about 20 or less, and X is an anionic counterion.
Cationic cellulose is available from Aimerchol Corp. (Edison, N.J., USA) in their Polymer JR (trade mark) and LR (trade mark) series of polymers, as salts of hydroxyethyl cellulose reacted with trimethyl ammonium substituted epoxide, referred to in the industry (CTFA) as Polyquaternium 10. Another type of cationic cellulose includes the polymeric quaternary ammonium salts of hydroxyethyl cellulose reacted with lauryl dimethyl ammonium-substituted epoxide, referred to in the industry (CTFA) as Polyquaternium 24. These materials are available from Amerchol Corp. (Edison, N.J., USA) under the tradename Polymer LM-200.
Other suitable cationic polysaccharide polymers include quaternary nitrogen-containing cellulose ethers (e.g. as described in U.S. Pat. No. 3,962,418), and copolymers of etherified cellulose and starch (e.g. as described in U.S. Pat. No. 3,958,581).
A particularly suitable type of cationic polysaccharide polymer that can be used is a cationic guar gum derivative, such as guar hydroxypropyltrimonium chloride (Commercially available from Rhodia (formerly Rhone-Poulenc) in their JAGUAR trademark series).
Examples are JAGUAR C13S and JAGUAR CB289, which have a low degree of substitution of the cationic groups and high viscosity. JAGUAR C15, having a moderate degree of substitution and a low viscosity, JAGUAR C17 (high degree of substitution, high viscosity), JAGUAR C16, which is a hydroxypropylated cationic guar derivative containing a low level of substituent groups as well as cationic quaternary ammonium groups, and JAGUAR 162 which is a high transparency, medium viscosity guar having a low degree of substitution.
Preferably the cationic deposition polymer is selected from cationic cellulose and cationic guar derivatives. Particularly preferred deposition polymers are JAGUAR C13S, JAGUAR CB289, JAGUAR C15, JAGUAR C17 and JAGUAR C16 and JAGUAR C162.
The cationic deposition polymer will generally be present at levels of from 0.001 to 5%, preferably from about 0.01 to 1%, more preferably from about 0.02% to about 0.5% by weight of the total composition.
Other Ingredients
The shampoo composition of the invention may further comprise from 0.1 to 5% by weight of the total composition of a silicone suspending agent. Examples are polyacrylic acids, cross linked polymers of acrylic acid, copolymers of acrylic acid with a hydrophobic monomer, copolymers of carboxylic acid-containing monomers and acrylic esters, cross-linked copolymers of acrylic acid and acrylate esters, heteropolysaccharide gums and crystalline long chain acyl derivatives. The long chain acyl derivative is desirably selected from ethylene glycol stearate, alkanolamides of fatty acids having from 16 to 22 carbon atoms and mixtures thereof. Ethylene glycol distearate and polyethylene glycol 3 distearate are preferred long chain acyl derivatives. Polyacrylic acid is available commercially as Carbopol 420, Carbopol 488 or Carbopol 493. Polymers of acrylic acid cross-linked with a polyfunctional agent may also be used, they are available commercially as Carbopol 910, Carbopol 934, Carbopol 940, Carbopol 941 and Carbonol 980. An example of a suitable copolymer of a carboxylic acid containing a monomer and acrylic acid esters is Carbopol 1342. All Carbopol materials are available from Goodrich and Carbopol is a trade mark.
Suitable cross linked polymers of acrylic acid and acrylate esters are Pemulen TRl or Pemulen TR2. A suitable heteropolysaccharide gum is xanthan gum, for example that available as Kelzan mu.
Compositions of this invention may contain any other ingredient normally used in hair treatment formulations. These other ingredients may include viscosity modifiers, preservatives, colouring agents, polyols such as glycerine and polypropylene glycol, chelating agents such as EDTA, antioxidants, fragrances, and sunscreens. Each of these ingredients will be present in an amount effective to accomplish its purpose. Generally these optional ingredients are included individually at a level of up to about 5% by weight of the total composition.
Preferably, compositions of this invention also contain adjuvants suitable for hair care. Generally such ingredients are included individually at a level of up to 2%, preferably up to 1%, by weight of the total composition.
Among suitable hair care adjuvants, are:
(i) natural hair root nutrients, such as amino acids and sugars. Examples of suitable amino acids include arginine, cysteine, glutamine, glutamic acid, isoleucine, leucine, methionine, serine and valine, and/or precursors and derivatives thereof. The amino acids may be added singly, in mixtures, or in the form of peptides, e.g. di- and tripeptides. The amino acids may also be added in the form of a protein hydrolysate, such as a keratin or collagen hydrolysate. Suitable sugars are glucose, dextrose and fructose. These may be added singly or in the form of, e.g. fruit extracts. A particularly preferred combination of natural hair root nutrients for inclusion in compositions of the invention is isoleucine and glucose. A particularly preferred amino acid nutrient is arginine.
(ii) hair fibre benefit agents. Examples are:
ceramides, for moisturising the fibre and maintaining cuticle integrity. Ceramides are available by extraction from natural sources, or as synthetic ceramides and pseudoceramides. A preferred ceramide is Ceramide II, ex Quest. Mixtures of ceramides may also be suitable, such as Ceramides LS, ex Laboratoires Serobiologiques.
The invention is further illustrated by way of the following non-limitative Examples:

Unilever Home and Personal Care USA, division of Conopco, Inc.