This invention relates to a silicone polymer that is insoluble in organic solvents due to its three dimensional crosslinked structure which swells up relative to fluorosilicone oils. The silicone polymer is a crosslinked product of an SiH containing fluorosilicone and an unsaturated polyoxyalkylene. This invention also relates to a paste-like composition formed by making the silicone compounds swell up in silicone oil and a cosmetic material.

This invention relates to a silicone polymer which is insoluble in organic solvents because it has a three-dimensional crosslinked structure which swells up relative to fluorosilicone oils, to a paste-like composition formed by making the silicone compounds swell up in silicone oil, and to a cosmetic material.
In various fields including that of cosmetic products, silicone oils have long been used as base oils on account of their safety.
In particular, with regard to skin care and make up, low viscosity silicone oils of 100 mm2/s are very popular on account of their excellent spreading properties, clean feel and high safety.
However, when for example a paste composition without fluidity is made up with a low viscosity silicone oil as base oil, the addition amount of thickener has to be increased, and consequently it is difficult to obtain a smooth, even composition. Moreover, the low viscosity silicone oil tends to separate and leak from the composition obtained, so stability was low. To solve this problem, organic materials such as dextrin fatty acid esters (Japanese Patent Laid-Open Sho 62-121764, 62-143971, 62-143970, 63-159489), cane sugar fatty acid esters (Japanese Patent Laid-Open Sho 63-235366), trimethylsilyl polyvinyl alcohol or trimethyl silyl oligosaccharides (Japanese Patent Laid-Open Sho 62-240335) and fatty acid ester group-containing cellulose ethers (Japanese Patent Laid-Open Sho 63-260955), or inorganic materials such as organically modified clay minerals (Japanese Patent Laid-Open Sho 62-45656, 62-54759, 63-72779), have been used as thickeners for low viscosity silicone oils.
However, when these organic or inorganic materials were used as thickeners, there was a problem in that the clean feel and high extendibility of the low viscosity silicone oil decline.
In this connection, a method was proposed obtain a uniform paste-like composition by using a specific silicone polymer as a thickener, and treating the low viscosity silicone oil under a shear force (Japanese Patent Laid-Open 2-43263).
However, in the field of cosmetic products, not only oil but also water must be blended with the composition as an essential component. In this case, surfactants are used according to the normal procedure, but it is difficult to disperse the silicone oil and water in a homogeneous, stable state. Also, although the silicone thickener disclosed in the aforesaid Japanese Patent Laid-Open 2-43263 has excellent thickening properties relative to the silicone oil, it does not disperse evenly when water is also blended in the composition. Moreover, some surfactants irritate the skin, and their use is therefore undesirable.
To solve this disadvantage, in Japanese Patent Laid-Open Hei 4-272932, and 5-140320, it was proposed to introduce a polyoxyalkylene group in the molecule of the silicone thickener.
At the same time, to improve the staying powers of the cosmetic material, it has been proposed to blend a silicone oil having excellent water repellence and oil repellence and a high fluorine content with the silicone oil. However, although these oils have a high water repellence and oil repellence, water and oil tend to separate from them in storage. Consequently, it was difficult to obtain a cosmetic material having excellent storage stability, and excellent functional properties when it was used on the skin.
It is therefore an object of this invention to provide a silicone polymer having a fluorine-modified oil with excellent water repellence and oil repellence as base oil, and which swells up relative to these oils, to a homogeneous paste-like composition using this silicone polymer, and to a cosmetic material comprising this composition.
This invention, which was discovered as a result of intensive studies performed to achieve the above object, is a silicone polymer having a three-dimensional crosslinked structure obtained by polymerizing at least one selected from the group consisting of an organohydrogen polysiloxane represented by the general formula (A1):
R1aR2bHcSiO(4xe2x88x92axe2x88x92bxe2x88x92c)/2,xe2x80x83xe2x80x83(A1)
and an organohydrogen polysiloxane represented by the general formula (A2):
R1dHeSiO(4xe2x88x92dxe2x88x92e)/2,xe2x80x83xe2x80x83(A2)
and at least one selected from the group consisting of a polyoxyalkylene represented by the following general formula (B1):
CfH2fxe2x88x9210(CgH2gO)nCfH2fxe2x88x921,xe2x80x83xe2x80x83(B1)
a polyoxyalkylene represented by the following general formula (B2):
a polyoxyalkylene represented the following general formula (B3):
and an organopolyoxy alkylene (B4) represented by the following general formula (B4):
R1jR5kSiO(4xe2x88x92jxe2x88x92k)/2,xe2x80x83xe2x80x83(B4)
which can contain (or dissolve and swell) its same weight or more of pentane-3,3,3-trifluoropropyl pentamethylcyclopentasiloxane (in the formula, R1, which may be the same or different, is a hydrocarbon group having 1 to 20 carbon atoms, which do not contain an aliphatic unsaturated bond and may be substituted or unsubstituted, whereof about 11 to 60 mole % is a fluorine-substituted monovalent hydrocarbon group, R2, which may be the same or different, is an organic group represented by the general formula xe2x80x94CfH2fO(CgH2gO)nR6, R3, which may be the same or different, is hydrogen atom or a monofunctional hydrocarbon group containing 1 to 10 carbon atoms which does not contain aliphatic unsaturated bonds and which may be substituted or unsubstituted, R4, which may be the same or different, is an organic group identical to R3 or represented by xe2x80x94CfH2fxe2x88x921, R5 is a monofunctional hydrocarbon group having 2 to 10 carbon atoms containing a terminal vinyl group, and R6 is a hydrogen atom or a monofunctional hydrocarbon group or acetyl group not containing aliphatic unsaturated groups, which may be substituted or and substituted, a is about 1.0-2.3, b is about 0.001 to 1.0, c is about 0.001-1.0, d is about 1.0-2.3, e is about 0.001-1.0, j is about 1.0-2.3, and k is about 0.001-1.0, and about 1.5xe2x89xa6a+b+cxe2x89xa6about 2.6, about 1.5xe2x89xa6d+exe2x89xa6about 2.6, about 1.5xe2x89xa6j+kxe2x89xa6about 2.6, f is an integer in the range 2-6, g is 2, 3 or 4, h is an integer in the range 1-200, i is an integer in the range 1-20, and x is 0 or 1. ).
The silicone polymer obtained by polymerizing the organohydrogen polysiloxane expressed by the above general formula (A2) and the organopolysiloxane expressed by the above general formula (B4), or the silicone polymer obtained by polymerizing the organohydrogen polysiloxane expressed by the above general formula (A2) and the polyoxyalkylene expressed by the above general formula (B1), are preferred.
The paste-like silicone composition obtained by kneading a mixture of 100 weight parts of the above silicone polymer and 10-1000 weight parts of a fluorine-modified silicone oil, which is represented by the general formula (C):
R1mSiO(4xe2x88x92m)/2xe2x80x83xe2x80x83(C)
having a viscosity of less than about 200 mm2/s at 25 degree C. (R1 may be identical or different, are monofunctional hydrocarbon groups having 1 to 20 carbon atoms not containing an aliphatic unsaturated bond which may be substituted or unsubstituted, whereof about 11-60 mole % is a fluorine-substituted monofunctional hydrocarbon group, and m is 1.8-2.3), is a homogeneous paste, and cosmetic materials containing this paste-like silicone composition have good stability and are very easy-to-use.
This invention provides a cosmetic material wherein the above paste-like silicone composition is blended, or a cosmetic material comprising this cosmetic material as a component, comprising a) the above paste-like silicone composition, b) an oil and c) a compound having an alcoholic hydroxyl group in the molecular structure, wherein the blending amount of the a) paste-like silicone composition in the cosmetic material is 0.1-70.0 wt %.
At least part of this b) oil may be a liquid at ordinary temperature, and it is preferred that at least part of the oil b) is selected from the group consisting of a silicone oil comprising a volatile silicone, and an oil having a repeating unit of xe2x80x94[Oxe2x80x94Sixe2x80x94]n in the molecular skeleton. Herein, the xe2x80x9coil having a repeating unit of xe2x80x94[Oxe2x80x94Sixe2x80x94]n in the molecular skeletonxe2x80x9d is an oil having a branched siloxane structure, which is a straight chain or cyclic silicone, whereof the major part comprises a xe2x80x94[Oxe2x80x94Sixe2x80x94]n skeleton and has a xe2x80x94Sixe2x80x94(CH2CH2)mxe2x80x94Sixe2x80x94 bond in part of the molecule.
The compound c) having an alcoholic hydroxyl group in the molecular structure is preferably a water-soluble, and monofunctional or polyfunctional alcohol. The blending amount of the above oil b) is preferably 0.1 to 50.0 wt %, and the blending amount of the compound c) having an alcoholic hydroxyl group in the molecular structure is preferably 0.1 to 70.0 wt %.
The cosmetic material may also contain at least one of d) water, e) a powder and/or colorant, f) a surfactant, g) a crosslinked organopolysiloxane not containing a fluorine-substituted alkyl group, h) a silicone resin, and i) an ultraviolet protection component.
At least part of the above e) powder and/or colorant is preferably at least one of a powder having a silicon resin and silicone elastomer as skeleton, and an organic powder having xe2x80x94[Oxe2x80x94Sixe2x80x94]nxe2x80x94 as structural repeating unit in the molecular skeleton.
The f) surfactant is preferably a modified silicone having a polyoxy alkylene chain in the molecule, examples of this modified silicone being preferably represented by the following general formula (D):
R3pR2qR7rSiO(4xe2x88x92pxe2x88x92r)/2xe2x80x83xe2x80x83(D)
(in the formula, R2 are identical or different, and are organic groups represented by the general formula xe2x80x94CfH2fO(CgH2gO)hR6, R3 is a hydrogen atom or a monofunctional hydrocarbon group having 1 to 10 carbon atoms not containing aliphatic unsaturated bonds, and which may be substituted or unsubstituted, R6 is a hydrogen atom or a monofunctional hydrocarbon group or acetone group not containing or aliphatic unsaturated groups and which may be substituted or unsubstituted, R7 is a fluorine-substituted monofunctional hydrocarbon group not containing aliphatic unsaturated bonds, p is about 1.0-2.0, q is about 0.001-1.0, r is about 0.001-1.0, and about 1.5:5xe2x89xa6p+q+rxe2x89xa6about 2.6). It is preferred that HLB of the g) surfactant is 1-18.
The g) crosslinked organopolysiloxane not containing fluorine-substituted alkyl groups preferably contains (or dissolves) at least its own weight of a silicone having a viscosity of 0.65-100 mm2/s, and swells up. It is more preferred that it is a crosslinked organopolysiloxane which forms a crosslinked structure by reacting an organopolysiloxane having at least an average of 1.5 vinylic reactive sites, and an organopolysiloxane having at least an average of 1.5 hydrogen atoms directly bonded to silicon atoms, in the molecule. In particular, it is further preferred that this g) crosslinked organopolysiloxane not containing fluorine-substituted alkyl groups is a crosslinked organopolysiloxane comprising at least one of a polyoxyalkyl part, alkyl part, alkenyl part and aryl part in the crosslinked molecule.
It is preferred that the h) silicone resin is an acrylic silicone, and more preferred that this acrylic silicone contains at least one of a pyrrolidone part, long chain alkyl part, polyoxyalkylene part and fluoroalkyl part in the molecule. Further, it is preferred that the h) silicone resin is a silicone lattice compound, and more preferred that this silicone lattice compound contains at least one of a pyrrolidone part, long chain alkyl part, polyoxyalkylene part, fluoroalkyl part and amino part.
This invention provides a skincare cosmetic, hair treatment cosmetic, antiperspirant, make-up or ultraviolet protection cosmetic, and further provides a cosmetic of this type in the form of a liquid, and emulsion, cream, solid, paste, gel, powder, laminate, mousse or spray.
Describing the invention now in more detail, the component (A1) is represented by the average empirical formula R1aR2bHcSiO(4xe2x88x92axe2x88x92bxe2x88x92b)/2 ((R1 may be identical or different, and are monofunctional hydrocarbon groups having 1 to 20 carbon atoms not containing an aliphatic unsaturated bond which may be substituted or unsubstituted, whereof 11-60 mole % is a fluorine-substituted monofunctional hydrocarbon group), R2 may be identical or different, and are organic groups represented by the general formula xe2x80x94CfH2fO(CgH2gO)hR6, a, b, c are integers satisfying the relations 1.0xe2x89xa6axe2x89xa62.3, 0.001xe2x89xa6bxe2x89xa61.0, 0.001xe2x89xa6cxe2x89xa61.0, 1.5xe2x89xa6a+b+cxe2x89xa62.6, f is an integer in the range 2-6, g is 2 and/or 3, and/or 4, h is an integer in the range 1-200, and R6 is a monofunctional hydrocarbon group or acetyl group not containing hydrogen atoms or aliphatic unsaturated groups, which may be substituted or unsubstituted).
Examples of R1 are alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl and decyl; saturated alicyclic hydrocarbons such as cyclopentyl and cyclohexyl; aryl groups such as phenyl and tolyl; and fluorine-substituted alkyl groups such as trifluoropropyl, nonafluorohexyl and heptadecylfluorodecyl, but methyl and trifluoropropyl are particularly to be preferred.
Of the organic groups R1, it is required that 11-60 mol % are fluorine-substituted monofunctional hydrocarbon groups. If the proportion is less than 11 mole %, swelling properties in the fluorine-substituted silicone oil which is component (C) become poorer, and if it exceeds 60 mol %, manufacture of the component (A1) is difficult. Preferably, the range is 20-50 mole %.
a is 1.0-2.3, but preferably 1.2-2.1. b is 0.001-1.0, but preferably 0.005-0.5. c is 0.001-1.0, but preferably 0.005-0.5. When a is less than 1.0, the degree of crosslinking is too high, so the polymer cannot contain its own weight or more of penta-3,3,3-trifluoropropyl pentamethyl cyclopentasiloxane, and when it is larger than 2.3, the degree of crosslinking is too low, so it is difficult to form the three-dimensional crosslinked structure. When b is less than 0.001, the hydrophilic properties are low, so it is difficult to form a water-in-oil (W/O) composition, and when it is larger than 1.0, hydrophilic properties are too high so it is again difficult to form a water-in-oil emulsion composition. When c is less than 0.001, the degree of crosslinking is low, so it is difficult to form a three-dimensional crosslinked structure, and when it is larger than 1.0, the degree of crosslinking is too high, so the polymer can no longer contain its own weight or more of penta-3,3,3-trifluoropropyl pentamethyl cyclopentasiloxane.
a+b+c is in the range 1.51-2.6, but preferably 1.8-2.2. f is in the range 2-6, but preferably 3-6. g is 2 and/or 3, and/or 4. At least one unit is selected from ethylene oxide, propylene oxide and butylene oxide, but ethylene oxide or a copolymer of ethylene oxide and propylene oxide is preferred. h is an integer in the range 1-200, but preferably 3-100. Examples of R6 are hydrogen, methyl, heptyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl and acetyl, but hydrogen or methyl are particularly preferred.
This organopolysiloxane may be straight chain, branched or cyclic, but to make the polymerization reaction proceed smoothly, it is preferred that it is straight chain or essentially straight chain, and partly contains branch units.
The component (A2) is represented by the average empirical formula R1dHeSiO(4xe2x88x92dxe2x88x92exe2x88x92)/2 (in the formula, R1 may be the same as above, and d, e are integers satisfying the relation 1.0xe2x89xa6dxe2x89xa62.3, 0.001xe2x89xa6exe2x89xa61.0).
d is 1.0-2.3, but preferably 1.2-2.1, and e is 0.001-1.0, but preferably 0.005-0.5. When d is less than 1.0, the degree of crosslinking is too high, so the polymer cannot contain its own weight or more of penta-3,3, 3-trifluoropropyl pentamethylcyclopentasiloxane. When it is larger than 2.3, the degree of crosslinking is too low, so it is difficult to form the three-dimensional crosslinked structure. When e is less than 0.001, the degree of crosslinking is too low, so it is difficult to form the three-dimensional crosslinked structure, and when it is larger than 1.0, the degree of crosslinking is too high, so the polymer can no longer contain its own weight or more of penta-3,3,3-trifluoropropyl pentamethylcyclopentasiloxane.
This organopolysiloxane may be straight chain, branched or cyclic, but to make the polymerization reaction proceed smoothly, it is preferred that it is straight chain or essentially straight chain, and partly contains branch units.
The component (B1) is represented by the average empirical formula CfH2fxe2x88x921(CgH2gO)CfH2fxe2x88x921 (in the formula, f, g and h are identical to the above).
The component (B2) has the average empirical formula:
(in the formula, R3 is a monofunctional hydrocarbon group of 1-10 carbon atoms not containing hydrogen atoms or aliphatic unsaturated group bonds, and which may be substituted or unsubstituted, f, g and h are identical to the above, and x is 0 or 1).
Examples of R3 are hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl and decyl, but hydrogen, methyl, ethyl and propyl are particularly preferred.
The component. (B2) may be obtained for example using glycerine or trimethyloylpropane as starting material by alkenyl etheration of the terminal groups.
All three polyoxyalkylene terminal groups are alkenyl etherated, but only two may be blocked by alkenyl ether, and and the remaining one left as a hydroxyl group.
If the component (B2) is obtained using glycerine monoallyl ether or trimethyloylpropane monoallyl ether as starting material by adding an alkenyl oxide and performing alkenyl etheration of the terminal groups, a structure is obtained containing two polyoxyalkylene units in the molecule and three terminal alkenyl groups in the molecule. This polyoxyalkylene compound may also be used.
The component (B3) may be represented by the average empirical formula:
(in the formula, R4 are organic groups which may be identical or different, and are identical to R3 or represented by xe2x80x94CfH2fxe2x88x921, f, g and h are identical to the above, and i is integer in the range 1-20).
i is 1-20, but preferably 2-10. When i is larger than 20, the degree of crosslinking is too high, so the polymer can no longer contain its own weight or more of penta-3,3,3-trifluoropropyl pentamethylcyclopentasiloxane.
The component (B3) may for example be obtained by adding an alkylene oxide and allyl glycidyl ether to a lower alcohol or allyl alcohol, or by alkylation or alkenyl etheration of terminal groups after the addition.
The component (B4) has the average empirical formula R1jR5kSiO(4xe2x88x92jxe2x88x92k)/2 (in the formula, R1 is identical to the above, R5 is a monofunctional hydrocarbon group having terminal vinyl groups, and j, k are integers satisfying the relations 1.0xe2x89xa6jxe2x89xa62.3, 0.001xe2x89xa6kxe2x89xa61.0). Examples of R5 are vinyl, allyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl and decenyl, but vinyl is preferred. j is 1.0-2.3, but preferably 1.2-2.1, k is 0.001-1.0, but preferably 0.005-0.5. When j is less than 1.0, the degree of crosslinking is too high, so the polymer can no longer contain its own weight or more of penta-3,3,3-trifluoropropyl pentamethyl cyclopentasiloxane. When it is larger than 2.3, the degree of crosslinking is too low, so it is difficult to form a three-dimensional crosslinked structure. When k is less than 0.001, the degree of crosslinking is too low, so it is difficult to form a three-dimensional crosslinked structure, and when it is larger than 1.0, the degree of crosslinking is too high, so the polymer can no longer contain its own weight or more of penta-3,3,3-trifluoropropyl pentamethyl cyclopentasiloxane.
This organopolysiloxane may be straight chain, branched or cyclic, but to make the polymerization reaction proceed smoothly, it is preferred that it is straight chain or essentially straight chain, and partly contains branch units.
The component (C) is represented by the average empirical formula R1mSiO(4xe2x88x92m)/2 (in the formula, R1 is identical to the above and m is an integer satisfying the relation 1.8xe2x89xa6mxe2x89xa652.3). m lies in the range 1.8-2.3, but preferably 1.9-2.1. This organopolysiloxane may be straight chain, branched or cyclic, but it is preferred that it is straight chain or essentially straight chain, and partly comprises a branch unit. It is particularly preferred that it is a fluorine-modified cyclic silicone represented by the formula:
(in the formula, y is an integer from 4-6).
This fluorine-modified silicone oil has a viscosity at 25 degree C. of 200 mm2/s, but preferably 20-180 mm2/s.
The silicone polymer of this invention may be obtained by polymerizing the organohydrogen polysiloxanes represented by (A1) and/or (A2); the polyoxy alkylenes represented by (B1) and/or (B2), and/or (B3), and/or the organopolysiloxane represented by (B4). By kneading this silicone polymer with the fluoride-modified silicone oil (C), a paste-like composition can be obtained. Alternatively, a paste-like composition can be obtained by manufacturing a silicone polymer by polymerizing a mixture comprising the organohydrogen polysiloxanes represented by (A1) and/or (A2), the polyoxy alkylenes represented by (B1) and/or (B2), and/or (B3), and/or the organopolysiloxane represented by (Be), and part of the fluorine-modified silicone oil (C), and kneading this silicone polymer with the remainder of the fluoride-modified silicone oil (C).
To obtain the silicone polymer of this invention, the reaction is performed at room temperature or higher temperature (approx. 50-120 degree C.) in the presence of a platinum compound (e.g., platinic chloride, alcohol-modified platinic chloride or platinic acid chloride-vinyl siloxane complex), or a rhodium compound.
When the reaction is performed, it may be in the absence of a solvent or an organic solvent may be used if necessary. Examples of organic solvents are aliphatic alcohols such as methanol, ethanol, 2-propanol and butanol; aromatic hydrocarbons such as benzene, toluene and xylene; aliphatic or alicyclic hydrocarbons such as n-pentane, n-hexane and cyclohexane; halogenated hydrocarbons such as dichloromethane, chloroform and carbon tetrachloride; and ketone-type solvents such as acetone and methyl ketone. However, due to the intended use in cosmetic products, it is preferred to conduct the reaction in the absence of a solvent, or in ethanol or 2-propanol.
The silicone compound of this invention comprises a three-dimensional crosslinked structure which is insoluble in organic solvents, i.e., it is insoluble in organic solvents comprising aliphatic organic solvents such as straight chain or branched pentanes, hexane, decane, dodecane, hexadecane and octadecane; aromatic organic solvents such as benzene, toluene and xylene; alcohol-type organic solvents such as methanol, ethanol, propanol, butanol, hexanol and decanol; halogenated organic solvents such as chloroform and carbon tetrachloride; ketone-type organic solvents such as acetone and methylethyl ketone, and silicone solvents such as low viscosity dimethyl polysiloxane, methylphenyl polysiloxane and cyclic dimethyl polysiloxane.
The silicone polymer of this invention can also contain at least its own weight pentane-3,3,3-trifluoropropyl pentamethylcyclopentasiloxane, and a method of confirming this will be described later.
In the manufacture of the silicone composition of this invention, when the silicone polymer (C) is kneaded with the fluorine-modified silicone oil, this may be accomplished by an ordinary stirrer, but it is preferably performed under a shear force. This is because the silicone polymer has a three-dimensional crosslinked structure insoluble in solvents and the silicone polymer and the component (C) do not blend together homogeneously, so a paste-like composition of smooth appearance must be obtained by supplying sufficient dispersion.
The kneading may be performed for example by a three roller roll mill, two roller mill, side grinder, colloid mill, Gowling homogeniser or Disper, but a three roller roll mill or a D spur are preferred.
The proportion of the silicone composition a) in the cosmetic material of this invention is in the range 0.1-70.0 wt %, but preferably 1.0 to 50.0 wt %. If it is less than 0.1%, the cosmetic material obtained using it does not have good storage stability, and if it exceeds 70.0%, it no longer has a clean feel when spread on the skin.
The oil b) which is a component of this invention may be any of the following. Examples of natural animal or vegetable oils and fats, and semi-synthetic oils and fats, are avocado oil, linseed oil, almond oil, Chinese wax, perilla oil, olive oil, cacao butter, kapok wax, kaya oil, carnauba wax, liver oil, candellila wax, beef tallow, beef foot oil, beef bone fat, hydrogenated beef tallow, apricot kernel oil, spermaceti, hydrogenated oil, wheat germ oil, sesame oil, rice germ oil, rice-bran oil, sugar cane wax, sasanqua oil, safflower oil, shea butter, Chinese tung oil, cinnamon oil, jojoba wax, shellac wax, turtle oil, soybean oil, tea seed oil, tsubaki oil, evening primrose oil, corn oil, lard, rape seed oil, Japanese tung oil, rice-bran wax, germ oil, horse fat, persic oil, palm oil, palm kernel oil, castor oil, hydrogenated castor oil, caster oil fatty acid methyl ester, sunflower oil, grape seed oil, bayberry wax, jojoba oil, macadamia nut oil, bees wax, mink oil, cottonseed oil, cotton wax, Japan wax, haze kernel oil, montan wax, coconut oil, hydrogenated coconut oil, tricoconut oil fatty acid glyceride, mutton-tallow, peanut oil, lanolin, liquid lanolin, reduced lanolin, lanolin alcohol, hard lanolin, lanolin acetate, lanolin fatty acid isopropyl, hexyl laurate, POE lanolin alcohol ether, POE lanolin alcohol acetate, lanolin fatty acid polyethylene glycol, POE hydrogenated lanolin alcohol ether, and egg yolk oil.
Examples of hydrocarbon oils include ozokerite, squalane, squalene, ceresine, paraffin, paraffin wax, liquid paraffin, pristane, polyisobutylene, microcrystalline wax and Vaseline.
Examples of higher fatty acids include lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, undecylenic acid, oleic acid, linoleic acid, linolenic acid, arachidonic acid, eicosapentaenoic acid (EPA), docosahexaenoic acid (DHA), isostearic acid and 12-hydroxystearic acid.
Examples of higher alcohols include lauryl alcohol, myristyl alcohol, palmityl alcohol, stearyl alcohol, behenyl alcohol, hexadecyl alcohol, oleyl alcohol, isostearyl alcohol, hexyldodecanol, octyldodecanol, cetostearyl alcohol, 2-decyltetradecinol, cholesterol, phytosterol, POE cholesterol ether, monostearyl glycerin ether (batyl alcohol) and monooleyl glyceryl ether (cerakyl alcohol).
Examples of ester oils include diisobutyl adipate, 2-hexyldecyl adipate, di-2-heptylundecyl adipate, N-alkylglycol monoisostearates, isocetyl isostearate, trimethylolpropane triisostearic acid ester, ethylene glycol di-2-ethylhexanoic acid ester, cetyl 2-ethylhexanoate, trimethylolpropane tri-2-ethylhexanoic acid ester, pentaerythritol tetra-2-ethylhexanoic acid ester, cetyl octanoate, octyldodecyl gum ester, oleyl oleate, octyldodecyl oleate, decyl oleate, neopentyl glycol dicapric acid ester, triethyl citrate, 2-ethylhexyl cinnamate, amyl acetate, ethyl acetate, butyl acetate, isocetyl stearate, butyl stearate, diisopropyl sebacate, di-2-ethylhexyl sebacate, cetyl lactate, myristyl lactate, isopropyl palmitate, 2-ethylhexyl palmitate, 2-hexyldecyl palmitate, 2-heptylundecyl palmitate, cholesteryl 12-hydroxystearate, dipentaerythritol fatty acid esters, isopropyl myristate, octyldodecyl myristate, 2-hexyldecyl myristate, myristyl myristate, hexyldecyl dimethylocanoate, ethyl laurate, hexyl laurate, N-lauroyl-L-glutaminic acid 2-octyldodecyl ester, diisostearyl malic acid, dextrin palmitic acid ester, dextrin stearic acid ester, dextrin 2-ethylhexanic acid palmitic acid ester, cane sugar palmitic acid ester, cane sugar stearic acid ester, monobenzylidene sorbitol and dibenzylidene sorbitol.
Examples of glyceride oils include acetoglyceride, diisooctanoic acid glyceride, triisostearic acid glyceride, triisopalmitic acidglyceride, tri-2-ethylhexanoic acid glyceride, monostearic acid glyceride, di-2-heptylundecanoic acid glyceride and trimyristic acid glyceride.
As examples of silicone oils, mention may be made of organopolysiloxanes of low to high viscosity such as dimethylpolysiloxane, methylphenyl-polysiloxane, methylhydrogenpolysiloxane and dimethylsiloxane-methylphenylsiloxane copolymer, cyclic siloxanes such as octamethylcyclotetrasiloxane, decamethylcyclopenta-siloxane, dodecamethylcyclohexasiloxane, tetramethyltetrahydrogencyclotetra-siloxane and tetramethyltetraphenylcyclotetrasiloxane; silicone gums such as high polymer gum dimethylpolysiloxane and gum dimethylsiloxane-methylphenyl siloxane copolymer; and cyclic siloxane solutions of silicone gums, trimethylsiloxysilicic acid and cyclic siloxane solutions of trimethylsiloxysilicic acid, higher alkoxy-modified silicones such as stearoxysilicone, higher fatty acid-modified silicones, alkyl-modified silicones, amino-modified silicones, fluorine-modified silicones, silicone resins and silicone rubbers.
As examples of fluorine-containing oils, mention may be made of perfluoropolyether, perfluorodecalin, perfluorooctane, fluorinated pitch and fluoroalcohols. One, two or more of these may be used as necessary.
The content of the oil b) in the cosmetic material this invention depends on the form of the cosmetic material, but lies in the range 0-50.0 wt %, and preferably 1.0-30 wt %. If this content is less than 0.1 wt %, the slippery feel and moisture-retaining effect of the oil b) cannot be obtained, and if it exceeds 50.0 wt %, storage stability declines.
Examples of the compound c) having an alcoholic hydroxyl group in the molecular structure, which is a component of this invention, are as follows.
Examples of alcohols are lower alcohols such as ethanol, propanol and isopropanol; polyfunctional alcohols such as ethylene glycol, propylene glycol 1,3-butylene glycol, glycerine and diglycerine; alcohols such as ethylene glycol monoalkyl ether and diethylene glycol monoethylether; sugar alcohols such as sorbitol and mannitol; and cholesterol, sitostearol, phytosterol and lanosterol.
The water-soluble polymer may be a vegetable polymer such as gum arabic, gum tragacanth, galactan, carob gum, guar gum, karaya gum, carrageenan, pectin, agar, quince seed (marmelo), starch (rice, corn, potato, wheat), algae colloid, tranto gum and locust bean gum, microorganism polymers such as xanthan gum, dextran, saccinoglucan and pullulan, animal polymers such as collagen, casein, albumin and gelatin, starch polymers such as carboxymethyl starch and methylhydroxypropyl starch, cellulose polymers such as methyl cellulose, ethyl cellulose, methylhydroxypropyl cellulose, carboxymethyl cellulose, hydroxymethyl cellulose, hydroxypropyl cellulose, cellulose nitrate, cellulose sodium sulfate, sodium carboxymethyl cellulose, crystalline cellulose, and cellulose powder, alginic acid polymers such as sodium alginate and alginic acid propyleneglycol ester, vinyl polymers such as polyvinylmethylether and carboxyvinyl polymer, polyoxyethylene polymers, polyoxyethylene polyoxypropylene copolymer polymers, acrylic polymers such as sodium polyacrylate, polyethyl acrylate and polyacrylamide, other synthetic water-soluble polymers such as polyethyleneimine and cation polymers, and inorganic water-soluble polymers such as bentonite, magnesium aluminium silicate, laponite, hectorite and silicic acid anhydride.
Moreover, film-forming agents such as polyvinyl alcohol and polyvinyl pyrrolidone are also included in these water-soluble polymers, one, two or more being used as necessary. The content of the alcoholic hydroxyl group-containing compound c) in the cosmetic material this invention depends on the form of the cosmetic material, but lies in the range 0.1-70.0 wt %, and preferably 1.0-50 wt %. If this content is less than 0.1 wt %, the moisture-retaining, antifungal and antibiotic effects of c) cannot be obtained, and if it exceeds 50.0 wt %, the cosmetic material becomes stickier which is undesirable for cosmetic material.
Water d) may also be added as a component to the cosmetic material of this invention if required. The content of the water d) in the cosmetic material of this invention is 0-90.0 weight %, the blending proportion varying according to the type of cosmetic material. A cosmetic material containing water d) may take the form of an aqueous solution, oil-in-water (O/W) emulsion, water-in-oil.(W/0) emulsion, or an O/W/O or W/O/W emulsion.
An excellent cosmetic material according to the invention may be obtained using only the components b)-e), but the following components f), g), h), i), j) may also be added as required.
The component f) is the powders and/or colorants mentioned below. If used for ordinary cosmetic materials, the powder can take any form (spheres, needles, plates, non-defined forms, scales, spindles), have any particle diameter (haze, powders, pigments) and any particle structure (porous, non-porous). Examples are inorganic powders, organic powders, surfactant metal salt powders, colored pigments, pearl pigments, metal powder pigment and natural colorants.
Examples of inorganic powders are titanium oxide, zirconium oxide, zinc oxide, cerium oxide, magnesium oxide, barium sulfate, calcium sulfate, magnesium sulfate, calcium carbonate, magnesium carbonate, talc, mica, kaolin, sericite, muscovite, synthetic mica, phlogopite, red mica, biotite, lithia mica, silicic acid, silicic acid anhydride, aluminium silicate, magnesium silicate, magnesium aluminium silicate, calcium silicate, barium silicate, strontium silicate, tungstic acid metal salts, hydroxyapatite, vermiculite, haidingerite, bentonite, montmorillonite, hectorite, zeolite, ceramic powder, calcium diphosphate, alumina, aluminium hydroxide, boron nitride and silica.
Examples of organic powders are polyamide powder, polyester powder, polyethylene powder, polypropylene powder, polystyrene powder, polyurethane, benzoguanamine powder, polymethyl-benzoguanamine powder, tetrafluoroethylene powder, polymethylmethacrylate powder, cellulose, silk powder, nylon powder, nylon 12, nylon 6, silicone powder, styrene-acrylic acid copolymer, divinylbenzene-styrene copolymer, vinyl resin, urea resin, phenol resin, fluororesin, silicone resin, acrylic resin, melamine resin, epoxy resin, polycarbonate resin, microcrystalline fiber powders, starch powder and lauroyl lysine.
Examples of surfactant metal salt powders (metallic soaps) are zinc stearate, aluminum stearate, calcium stearate, magnesium stearate, zinc myristate, magnesium myristate, zinc cetyl phosphorate, calcium cetyl phosphate and zinc sodium cetyl phosphate.
Examples of colored pigments are inorganic red pigments such as ferric oxide, iron hydroxide and ferric titanate, inorganic brown pigments such as gamma-iron oxide, inorganic yellow pigments such as yellow iron oxide and ochre, inorganic black pigments such as black iron oxide and carbon black, inorganic purple pigments such as manganese violet and cobalt violet, inorganic green pigments such as chromium hydroxide, chromium oxide, cobalt oxide and cobalt titanate, inorganic blue pigments such as cobalt and titanic acid cobalt, Prussian blue and ultramarine blue, tar colorant lake, natural colorant lake, and synthetic resin powders comprising combinations of these powders.
Examples of pearl pigments are titanium oxide-coated mica, titanium oxide-coated mica, bismuth oxychloride, titanium oxide-coated bismuth oxychloride, titanium oxide-coated talc, scales foil and titanium oxide-coated colored mica; examples of metal powder pigments are aluminium powder, copper powder and stainless steel powder.
Examples of tar colorants are Red No. 3, Red No. 104, Red No. 106, Red No. 201, Red No. 202, Red No. 204, Red No. 205, Red No. 220, Red No. 226, Red No. 227, Red No. 228, Red No. 230, Red No. 401, Red No. 505, Yellow No. 4, Yellow No. 5, Yellow No. 202, Yellow No. 203, Yellow No. 204, Yellow No. 401, Blue No. 1, Blue No. 2, Blue No. 201, Blue No. 404, Green No. 3, Green No. 201, Green No. 204, Green No. 205, Orange No. 201, Orange No. 203, Orange No. 204, Orange No. 206 and Orange No. 207; examples of natural colorants are powders chosen from carminic acid, laccaic acid, carthamine, brazilin and crocin.
To the extent that it does not interfere with the purpose of this invention, complexes of these powders, or materials processed with common oil bases, silicone oils, fluorine compounds and surfactants may also be used if necessary.
Various types of surface pretreatment may or may not be performed such as for example fluorine compound treatment, silicone resin treatment, pendant treatment, silane coupling agent treatment, titanium coupling agent treatment, oil base treatment, N-acylation lysine treatment, polyacrylic acid treatment, metallic soap treatment, aminoacid treatment, anhydride treatment, plasma treatment or mechano-chemical treatment. One, two or more of the above may be used as required.
The blending proportion of the powder used depends on the form of the cosmetic material, but it is 0.1 to 50 wt %, and preferably 0.5 to 30 wt %, relative to the total weight of cosmetic material.
Of these powders, elastomers such as silicone elastomer spherical powder, polyethylene powder, polypropylene powder, poly tetrafluoroethylene powder, silicone gum powder and polyurethane powder are preferred, as the product is then stable over time and its feel improves.
The component f) is the surfactants shown below.
The surfactant may be anionic, cationic, non-ionic or amphoteric, there being no limitation thereupon provided it is used in ordinary cosmetic materials.
Specific examples of anionic surfactants are fatty acid soaps such as sodium stearate and triethanolamine palmitate, alkyl ether carboxylic acids and their salts, condensate salts of aminoacids and fatty acids, alkane sulfonates, alkene sulfonates, sulfonates of fatty acid esters, sulfonates of fatty acid amides, formalin condensation sulfonates, sulfate ester salts such as alkylsulfate ester salts, secondary higher alcohol sulfate ester salts, alkyl and allyl ether sulfate ester salts, sulfate ester salts of fatty acid esters, sulfate ester salts of fatty acid alkyloylamides and Turkey red oil, alkylphosphates, ether phosphates, alkyl allyl ether phosphates, amide phosphates and N-acyl aminoacid activators.
Specific examples of cationic surfactants are amino salts such as alkylamine salts, polyamines and aminoalcohol fatty acid derivatives, alkyl quartenary ammonium salts, aromatic quartenary ammonium salts, pyridium salts and imidazolium salts.
Examples of non-ionic surfactants are sorbitan fatty acid esters, glycerol fatty acid esters, polyglycerol fatty acid esters, propylene glycol fatty acid esters, polyethylene glycol fatty acid esters, cane sugar fatty acid esters, polyoxyethylene alkyl ethers, polyoxypropylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, polyoxyethylene glycerol fatty acid esters, polyoxyethylene propylene glycol fatty acid esters, polyoxyethylene castor oil, polyoxyethylene hardened castor oil, polyoxyethylene phytostanol ether, polyoxyethylene phytosterol ether, polyoxyethylene cholestanol ether, polyoxyethylene cholesterol ether, polyoxyalkylene-modified organopolysiloxanes, polyoxy-alkylenealkyl co-modified organopolysiloxanes, alkanol-amides, sugar ether and sugar amides.
Of non-ionic surfactants, the fluoroalkyl group-containing polyether-modified silicone represented by the average empirical formula R3pR2qR7rSiO(4xe2x88x92pxe2x88x92qxe2x88x92r)/2 is preferred (R3 and R2 are the same as that of the above among a formula. R7 is a fluorine-substituted monofunctional hydrocarbon having 1-10 carbon atoms which do not have an aliphatic unsaturated bond, and p, q, r are integers satisfying the relations 1.0xe2x89xa6pxe2x89xa62.0, 0.001xe2x89xa6qxe2x89xa61.0, 0.00xe2x89xa6rxe2x89xa61.0, and 1.5xe2x89xa6p+q+rxe2x89xa62.6, respectively).
Examples of R7 are fluorine-substituted alkyl groups such as trifluoropropyl, nonafluorohexyl and heptadecylfluorodecyl, but trifluoropropyl is to be preferred.
p is 1.0-2.0, but preferably 1.2-1,9, q is 0.001-1.0, but preferably 0.005-0.5, and r is 0.001-1.0, but preferably 0.005-0.5. When p is less than 1.0, manufacture of this component is difficult, whereas if p exceeds 2.0, the fluorine-substituted alkyl group content is too low or hydrophilic properties are too low, so sufficient emulsification is no longer obtained. When q is less than 0.001, hydrophilic properties are too low, so sufficient emulsification is no longer obtained, and if it exceeds 1.0, manufacture of this component is difficult or, as the fluorine-substituted alkyl group content is too low, sufficient emulsification is again no longer obtained. When r is less than 0.001, hydrophilic properties are too low, the fluorine-substituted alkyl group content is too low, so sufficient emulsification is no longer obtained, and if it exceeds 1.0, manufacture of this component is difficult.
Examples of amphoteric surfactants are betaine, amino carboxylates and imidazoline derivatives. The blending amount relative to the surfactant is preferably 0.1-20 wt % and more preferably 0.5-10 wt % relative to the total amount of cosmetic material.
The component g) is a crosslinked organopolysiloxane which does not have a fluorine-substituted alkyl group, and it is preferred that this crosslinked organopolysiloxane contains more than its own weight of low viscosity silicone relative to silicone having a low viscosity of 0.65-100 mm2/s. It is also preferred that the crosslinked organopolysiloxane is formed by reacting an organopolysiloxane having on average at least 1.5 vinylic reactive sites in the molecule, and an organohydrogen polysiloxane having at least 1.5 hydrogen atoms directly bonded to silicon atoms. Further, it is preferred that the crosslinked organopolysiloxane which does not contain this fluorine-substituted alkyl group, contains at least one species chosen from a group comprising a polyoxyalkylene part, an alkyl part, an alkenyl part, an aryl part or a fluoroalkyl part in the crosslinked molecule.
The blending amount of the crosslinked organopolysiloxane in use is preferably 0.1-30.0 wt %, but more preferably 1.0-10.0 wt %, relative to the total weight of cosmetic material.
The component h) is a silicone resin such as an acrylic/silicone graft or block copolymer, or a silicone lattice compound, but is preferably an acrylic silicone resin.
It is particularly preferred that this silicone resin is an acrylic silicone resin which contains at least one species chosen from a group comprising a pyrolidone part, a long chain alkyl part, a polyoxyalkylene part and a fluoroalkyl part in the molecule. This silicone resin is preferably a silicone lattice compound. The blending proportion of the silicone resin, which is an acrylic/silicone graft or block copolymer, or a silicone lattice compound, is 1.0-10.0 wt %, and more preferably 1.0-10 wt %, relative to the total amount of cosmetic material.
The component i) is an ultraviolet defense component which in addition to the ultraviolet dispersants such as inorganic pigments and metal powders mentioned above, may also be an organic ultraviolet absorber. Specific examples are benzoic acid ester ultraviolet absorbers such as p-aminobenzoic acid, ethyl p-aminobenzoate, glyceryl p-aminobenzoate, amyl p-diaminomethyl aminobenzoate, octyl p-dimethyl aminobenzoate and ethyl 4-[N,N-di(2-hydroxy propyl)] aminobenzoate; salicylic acid ultraviolet absorbers such as methyl salicylate, salicylic acid ethylene glycol, phenyl salicylate, octyl salicylate, benzyl salicylate, p-tert-butylphenyl salicylate and homomenthyl salicylate; cinnamic acid ultraviolet absorbers such as benzyl cinnamate, 2-ethoxyethyl p-methoxycinnamate, octyl p-methoxycinnamate, and di-p-methoxycinnamic acid mono-2-ethylhexanoic acid glyceride; urocanic acid ultraviolet absorbers such as urocanic acid and ethyl urocanate; benzophenone ultraviolet absorbers such as hydroxymethoxybenzophenone, hydroxymethoxybenzophenone sulfonate, sodium hydroxymethoxy benzophenone sulfonate, dihydroxy methoxybenzophenone, sodium dihydroxydimethoxybenzophenone sulfonate, 2,4-dihydroxybenzophenone and tetrahydroxybenzophenone; dibenzoylmethane ultraviolet absorbers such as 4-tert-butyl-4-methoxydibenzoylmethane; anthranilic acid ultraviolet absorbers such as menthyl anthranilate, and benzotriazol derivatives such as 2-(2-hydroxy-5-methyl phenyl) benzotriazol, and polymer derivatives, silane, or siloxane derivatives of these molecules.
The blending proportion of these ultraviolet absorbers is preferably 0.1-20.0 wt % but more preferably 1.0-10.0 wt % relative to the total amount of cosmetic material. Moreover, of these organic ultraviolet absorbers, 2-ethylhexyl p-methoxycinnamate and 4-t-butyl-4xe2x80x2-methoxydibenzoylmethane are particularly to be preferred.
It is possible to use organic ultraviolet absorbers sealed in a polymer powder, and the polymer powder may also be hollow. The average first order particle diameter of the polymer powder is preferably in the range 0.1-50 xcexcm, and the particle size distribution may be broad or sharp. The type of polymer may be an acrylic resin, methacrylic resin, styrene resin, urethane resin, polyethylene resin, polypropylene resin, polyethylene terephthalate resin, silicone resin, Nylon or acrylamide resin. It is preferred that these polymer powders incorporate an organic ultraviolet absorber in a weight range of 0.1-30.0 wt % of the weight of powder, and it is particularly preferred to blend in 4-t-butyl-4xe2x80x2-methoxydibenzoylmethane which is a UVA absorber.
To the extent that they do not impair the effect of this invention, the components usually used in cosmetic materials may also be used in the cosmetic material of this invention, such as skin-forming agents, oil-soluble gelatinizers, organic-modified clay minerals, resins, ultraviolet absorbers, moisturizers, preservatives, antiseptics, antibacterials, perfumes, salts, antioxidants, pH regulators, chelating agents, refrigerants, anti-inflammatory agents, skin beautifying agents (whiteners, cell activators, dry and rough skin improvement agents, blood circulation promoters, skin astringents and anti-sebarrhoica agents), vitamins, aminoacids, nucleic acids, hormones and clathrates.
Examples of oil-soluble gelatinizers are metal soaps such as aluminium stearate, magnesium stearate and zinc myristate, aminoacid derivatives such as N-lauroyl-L-glutamic acid and alpha, gamma-di-n-butylamine, dextrin fatty acid esters such as dextrin palmitic acid ester, dextrin stearic acid ester and dextrin 2-ethyl hexanoic acid palmitic acid ester, cane sugar fatty acid esters such as cane sugar palmitic acid ester and cane sugar stearic acid ester, benzylidene derivatives of sorbitol such as monobenzylidene sorbitol and dibenzylidene sorbitol, and organic-modified clay minerals such as dimethylbenzyldodecylammonium montmorillonite clay and dimethyl dioctadecylammonium montmorillonite clay, one, two or more of these agents being used as necessary.
Examples of moisturizers are glycerol, sorbitol, propylene glycol, dipropylene glycol, 1,3-butylene glycol, glucose, xylitol, maltitol, polyethylene glycol, hyaluronic acid, chondroitin sulfate, pyrolidone carboxylate, polyoxyethylene methyl glucoside and polyoxypropylene methyl glucoside.
Examples of antiseptics and preservatives are paraoxybenzoic acid alkyl ester, benzoic acid, sodium benzoate, sorbic acid, potassium sorbate and phenoxyethanol; examples of antibacterials are benzoic acid, salicylic acid, carbolic acid, sorbic acid, paraoxy-benzoic acid alkyl ester, parachloro meta-cresol, hexachlorophene, benzalkonium chloride, chlorohexidine chloride, trichloro-carbanilide, photosensitizers and phenoxyethanol.
Examples of antioxidants are tocopherol, butylated hydroxyanisole, dibutylhydroxytoluene and phytic acid; examples of pH regulators are lactic acid, citric acid, glycolic acid, succinic acid, tartaric acid, dl-malic acid, potassium carbonate, sodium bicarbonate and ammonium bicarbonate; examples of chelating agents are alanine, ethylene diamine tetraacetic acid sodium salt, sodium polyphosphate, sodium metaphosphate and phosphoric acid; examples of refrigerants are L-menthol and camphor; examples of anti-inflammatory agents are allantoin, glycylrrhzin and its salts, glycyrrhetinic acid and glycyrrhetinic acid stearyl ester, tranexamic acid and azulene.
Skin beautifier components are whiteners such as placenta extract, arbutin, glutathione and creeping saxifrage extract; cell activators such as royal jelly, photosensitizers, cholesterol derivatives, and calf""s blood extract; dry, rough skin improvement agents; blood circulation promoters such as nonyl acid warenylamide, nicotinic acid benzyl ester, nicotinic acid beta-butoxyethyl ester, capsaicin, zingerone, cantharis tincture, ichthammol, caffeine, tannic acid, alpha, borneol, nicotinic acid tocopherol, inositol hexanicotinate, cyclandelate, cinnarizine, tolazoline, acetylcholine, verapamil, cepharanthin and gamma-orizanol, skin astringents such as zinc oxide and tannic acid, and anti-sebarrhoica agents such as sulfur and thianthol.
Examples of vitamins are vitamin A such as vitamin A oil, retinol, retinal acetate and retinal palmitate; vitamin B, i.e, vitamin B2 such as riboflavin, riboflavin butyrate, flavin adenine nucleotide; vitamin B6 such as pyridoxine hydrochloride, pyridoxine dioctanoate and pyridoxine tripalmitate; vitamin B12 and its derivatives, and vitamin B15 and its derivatives; vitamin C such as L-ascorbic acid, L-ascorbic acid dipalmitic acid ester, L-ascorbic acid-2-sodium sulfate and dipotassium L-ascorbic acid phosphoric acid diester; vitamin D such as ergocalciferol and cholecalciferol; vitamin E such as alpha-tocopherol, beta-tocopherol, gamma-tocopherol, acetic acid dl-alpha-tocopherol, nicotinic acid dl-alpha-tocopherol and succinic acid dl-alpha-tocopherol; vitamin H, vitamin P, nicotinic acids such as nicotinic acid, benzyl nicotinate and nicotinamide, pantothenic acids such as calcium pantothenate, D-pantothenyl alcohol, pantothenyl ethyl ether and acetyl pantothenyl ethyl ether, and biotin.
Examples of amino acids are glycine, valine, leucine, isoleucine, serine, threonine, phenylalanine, arginine, lysine, aspartic acid, glutamic acid, cystine, cysteine, methionine and tryptophan; examples of nucleic acids are deoxyribonucleic acid; and examples of hormones are estradiol and ethenyl estradiol.
Examples of astringent components are aluminium chlorohydrate and aluminium zirconium chlorohydrate, specific examples being Microdry UIF, REACH 101, REACH REACH 103, REACH 301, REACH 301 solution, REACH 501, REACH 501 solution, REHYDROL II, REACH AZP 902, REACH AZP 908, REACH AZP 855, REACH AZZ 902, REACH AZZ 855, REACH AZN 885, REZAL 36P, REZAL 36P solution, REZAL 36GP, REZAL 36G solution, REZAL 67P and REZAL 67 solution (product of REHEIS Co.).
There is no particular limitation on the applications of the cosmetic material of this invention, i.e., skincare products, hair products, antiperspirant products, makeup products, ultraviolet protection products and perfume solvents. Specific examples are basic cosmetic materials such as emulsions, creams, lotions, calamine lotion, sunscreens, sun tan agents, aftershave lotion, preshave lotion, packs, cleansing materials, face washing materials, anti-acne cosmetic materials and essences; makeup materials such as foundations, white powders, eye shadow, eyeliners, eye blow, cheek, lipstick and nail colors; and shampoos, rinses, conditioners, haircare, hair tonics, setting agents, body powders, deodorants, depilation agents, soaps, body shampoos, bath salts, hand soaps and perfumes. There is no particular limitation on the form of the product, which may be a liquid, emulsion, cream, solid, paste, gel, powder, laminate, mousse or spray.
The silicone polymer of this invention has water repellence, oil repellence, swells up relative to fluorine-modified silicone oils having a high fluorine-substituted alkyl group content, and forms a homogeneous paste-like composition. Further, cosmetic materials with which this composition is blended allow stable dispersion of fluorine-modified silicone oils, do not easily separate and feel very clean to use. Even when water is blended to form an emulsion, the target emulsion can easily be obtained, and a cosmetic material wherefrom water does not separate on storage and which has excellent stability can be obtained.

Silicone polymer, silicone composition, and cosmetic preparation containing the same


The present invention relates to an absorbent article having a body-facing surface and a transverse centerline, comprising; a hydrophilic topsheet, a backsheet joined to the topsheet, and an absorbent core disposed between the topsheet and the backsheet, and a lateral topsheet on each longitudinal side of the body-facing surface of the absorbent article so that at least a part thereof covers the topsheet where the topsheet covers the absorbent core, wherein the lateral topsheet comprises an embedded zone along the longitudinal direction of the absorbent article comprising a plurality of compressed areas where the lateral topsheet and the topsheet are jointly compressed so that the lateral topsheet is embedded into the topsheet, and wherein the lateral topsheet in the compressed areas is one layer.

Absorbent articles such as sanitary napkins are used by women during their menstrual periods to receive and contain blood discharges from the vagina. In addition to collecting body fluids like menses, these articles are also expected to protect the wearer's undergarment from body fluid contamination.
As absorbent articles are normally placed between the wearer's crotch and her undergarment, they can be easily deformed by motion of the wearer which often causes leakage of body fluid toward laterally opposed edges of the absorbent article. One approach to resolve a side leakage concern is to provide an absorbent article with side sheets, especially hydrophobic side sheets, in the side edges of an absorbent body of the absorbent article. The side sheets are bonded with a topsheet and/or a backsheet by a bonding method such as heat-sealing and heat-embossing, etc. Japanese patent laid-open No. 2009-11686 discloses absorbent articles having hydrophobic side sheets with folded inner ends which may be spaced apart from a topsheet. These articles, by having side sheets with folded inner ends which may be spaced apart from a topsheet, are intended to prevent the fluid like menstrual blood from bleeding on the side sheets separated from a topsheet when a large amount of fluid spreads out to the width of the topsheet the central portion of the absorbent articles. Absorbent articles disclosed in the reference mentioned above would effectively prevent body fluids reached on a topsheet of the absorbent article from leaking laterally, however, there is still unsolved problem that when the body fluid is placed on top of the side sheets, the hydrophobic side sheets folded and spaced from a topsheet cannot prevent the fluid effectively go into the product, thus leading to fluid leakage.
There is therefore a need for an absorbent article providing more effective side leakage prevention.

Absorbent article with embedded lateral topsheets


An analog switch includes an input terminal, an output terminal, a common gate, and a common source. The switch includes a current source which has a first input coupled to a first voltage supply, a control input coupled to receive a gate boost signal, and an output coupled to the common gate. The current source supplies a boost gate current to the common gate during a boost period and supplies a reduced gate current during a second period different than the boost period. The switch includes a clamp circuit which has a first terminal coupled to the common gate, a second terminal coupled to the common source, and a third terminal. The switch includes a Vgs detection circuit which provides the gate boost signal responsive to a conduction of current through the clamp circuit.

Analog signal switches are used to aggregate inputs and outputs from multiple sources into a signal chain for processing. For example, in a commercial HVAC system, input signals from several temperature sensors may be multiplexed via an analog switch into a single amplifier or an analog-to-digital (A/D) converter. Reducing the turn on time of an analog switch and enhancing its "on" resistance flatness to reduce errors in a signal chain are desired.

Analog switch with boost current for fast turn on


The presented application is a method for enabling verifiable trust in collaborative data sharing environments. The architecture supports the human-in-the-loop paradigm by establishing trust between participants, including human researchers and AI systems, by making all data transformations transparent and verifiable by all participants.

The era of immense data analytics is transforming health care with the ability to interpret large and diverse datasets to provide better diagnoses, manage complex diseases, improve efficiency of care, and generate aggregated data for Artificial Intelligence (AI) systems [1]. For instance, Alphabet, the parent company of Google, has launched a new initiative called Cityblock Health that will provide low income households with medical care by analyzing multiple datasets to determine where care is needed [1]. Furthermore, IBM Watson's cognitive computing platform uses multiple large datasets to generate predictive analytics for improved diagnoses. In both examples, individuals (or patients) are actively and continuously involved in contributing data to be fed to the AI systems and the research goal is achieved through an intense (sometimes real time) collaboration between humans (as the data contributors), diverse researchers from multiple disciplines (e.g., medicine, computer science, statistics) and AI systems. The active involvement of humans (or patients) in this type of emerging health research is different to their roles in the classical clinical trial type research where a limited number of patients are involved and the patient's connection to the research ends when the data collection step is over. For data analytics health research, a feedback loop among patients, researchers and AI systems needs to be maintained in order to improve the predictive model. However, a successful realization of such a human-in-the-loop paradigm for health research requires establishing verifiable trust among participants (including humans and AI systems). The following motivating scenario reveals the challenges in maintaining trust among participants.
As part of a multi-disciplinary research team, the inventors are currently developing an active classifier to predict a patients' specific health. The classifier is active since the machine learning model will be constantly refined as individuals contribute their data points. Then the next patient at the point of care will benefit from the updated risk assessment model while she has a chance to contribute her data for the consequent model refinement iteration. Such a complex collaboration on private data requires multiple Data Sharing Agreements (DSA) to be devised between diverse groups of researchers and hospitals as each participant may adhere to different privacy policies and jurisdictions. In addition, patients are in the loop of research since the AI system needs to be updated in near real time to produce accurate and relevant cancer risk assessment for each patient [2], [3]. FIG. 1 conceptualizes the collaborative research pipeline for such a scenario, where hospitals h0, hn provide data for participants and multiple researchers r0, rn and AI systems a0, . . . , an provide data analytics on the datasets. Hospitals continuously provide data as it is generated, and DSA0, . . . , DSAn govern access to the datasets in the research pipeline. Auditing the data lifecycle (from collection to use, disclosure and transformation) is essential in this scenario to ensure accountability. Typically, local and global auditors oversee the process [4], and the trust between different auditors and researchers is a presumption, however in reality there are conflicts of interests that may undermine the presumed trust [5].
A trusted system means that all parties accept the actions of the system to be correct, the system's outputs to be true, and that the system will complete its expected task [6]. The trustworthiness of a system depends on the level of perceived trust of each system component [7]. Typically, trust is a subjective measurement based on the perception of how different parties evaluate each other and the systems they interact with. Achieving a trustworthy system requires transforming the notion of trust into an objective measurement. This transformation often relies on the use of a centralized trusted third party, where all collaborating parties trust this external entity (e.g., certificate authorities in public key infrastructures [8], arbitrated protocols [9]). Establishing trust through a centralized third party is often the source of collusion, which threatens the trust, the very central notion that collaborative parties intend to establish. The Enron Scandal [10] is a textbook case when the trust placed in the centralized auditors was a major factor in the fraud. Rather than a centralized approach, we can leverage a distributed system to support trust between collaborating parties and alleviate the disadvantages that tend to threaten trust in centralized systems.

Method for enabling trust in collaborative research


Operation noise and charge error of a charge pump circuit are reduced, thereby the jitter characteristics and the spectrum characteristics of a PLL circuit are improved, and further a time period elapsed until the PLL circuit is locked is shortened. The charge pump circuit 36 receives a control signal depending on an output of a phase comparison circuit 34 from a control circuit 35, and comprises a first P-channel MOS transistor P1, a second P-channel MOS transistor P2 and a third P-channel MOS transistor P3, and a first N-channel MOS transistor N1, a second N-channel MOS transistor N2 and a third N-channel MOS transistor N3, and a first current source 61, a second current source 62, a third current source 63 and a fourth current source 64. The transistor P1 is turned on and off by an up-signal of the phase comparison circuit 34, and the transistor N1 is turned on and off by a down-signal of it, and each of the transistor P2, the transistor P3, the transistor N2 and the transistor N3 is turned on and off on the basis of the control signal of the control circuit 35, an output signal from a VCO control terminal 65 is input to a VCO 8 through a low pass filter 37 while causing current to flow through the charge pump circuit 36.

1. Field of the Invention
The present invention relates to a current output type charge pump circuit and a PLL circuit using the charge pump circuit.
2. Related Background Art
A Phase-Locked Loop(PLL) circuit using a conventional charge pump circuit is shown in FIG. 1. The PLL circuit is so configured that a phase difference between a signal obtained by dividing a signal with the predetermined frequency generated from a reference signal source using an R counter and a signal obtained by dividing a signal of a voltage controlled oscillator circuit(VCO) using an N counter is detected by a phase comparison circuit, an up-signal and a down-signal depending on the phase difference from the phase comparison circuit carry out on and off switching of a MOS transistor 3 and a MOS transistor 4 between a current sources 1 and a current source 2 respectively connected to a power supply terminal and a ground terminal, and the signal output by on and off of the MOS transistors is smoothed by a low pass filter (LPF) connected to the VCO control terminal 9 and is input to the VCO.
According to the PLL circuit shown in FIG. 1, current flowing through the charge pump circuit is approximately zero in a state where both the up-signal and the down-signal turn the MOS transistor 3 and the MOS transistor 4 off (hereinafter referred to as a hold state), while current Ip flows through the charge pump circuit in a state where the up-signal turns the MOS transistor 3 on and the down-signal turns the MOS transistor 4 off (hereinafter referred to as a charge state), in a state where the up-signal turns the MOS transistor 3 off and the down-signal turns the MOS transistor 4 on (hereinafter referred to as a discharge state), and in a state where both the up-signal and the down-signal turn the MOS transistor 3 and the MOS transistor 4 on (hereinafter referred to as a charge/discharge state). Therefore, the current flowing through the charge pump circuit is changed by an on/off operation of each of the MOS transistor 3 and the MOS transistor 4 by the up-signal and the down-signal. Thus, the operation noise of the charge pump circuit is put on a power supply, which may adversely affect the jitter characteristics and the spectrum characteristics of the whole PLL circuit.
In the hold state, a potential at a source 5 of the MOS transistor 3 is approximately equal to a power supply potential, and a potential at a source 6 of the MOS transistor 4 is approximately equal to a ground potential. Here, assuming that the operating state of the PLL circuit is close to a lock state where the phase difference between the signal obtained by dividing the signal of the VCO using the N counter and the signal obtained by dividing the signal with the predetermined frequency generated from the reference signal source using the R counter is zero, a potential at the VCO control terminal 9 is close to an intermediate potential between the potential at the source 5 of the MOS transistor 3 and the potential at the source 6 of the MOS transistor 4. Since a parasitic capacitance 7 and a parasitic capacitance 8 exist in the current source 1 and the current source 2 respectively, in a case where the transition from the hold state to the charge state occurs, charges may flow from the parasitic capacitance 7 in the current source 1 due to a potential difference between the potential at the source 5 of the MOS transistor 3 and the potential at the VCO control terminal 9, and current which is more than current Ip may instantaneously flow into the VCO control terminal 9 (hereinafter referred to as a charge error). Similarly in a case where the transition from the hold state to the discharge state and the charge/discharge state occurs, the charge error caused by sharing charges may occur between the source 6 of the MOS transistor 4 and the VCO control terminal 9. When the charge error occurs, bigger current than current intended by a designer instantaneously flows, which may adversely affect the jitter characteristics, etc of the PLL circuit.
In another conventional example of the PLL circuit shown in FIG. 2, the potential at 15 and the potential 16 are controlled to be equal to the potential at an output terminal 17 by a voltage follower when both the MOS transistor 3 and the MOS transistor 4 are off in addition to the operations shown in FIG. 1. According to the PLL circuit shown in FIG. 2, as to a charge error, since the potential at 15 and the potential at 16 in a hold state are approximately equal to the potential at the output terminal 17, the charge error can be restrained. However, an operational amplifier 18 having a sufficient driving capability is required, so that a wide layout area is adversely required.
According to the PLL circuit shown in FIG. 1 and FIG. 2, described above, the value of Ip cannot be increased to improve the phase margin and the jitter characteristics of the PLL circuit in the lock state. Further, current for charging or discharging a capacitance 20 is restricted by a resistor 19, so that it takes a lot of time until the PLL circuit is in the lock state.
See Japanese Unexamined Patent Application No. 2000-36741, and an article entitled "A variable Delay Line PLL for CPU-Coprocessor Synchronization", US, IEEE Journal of Solid-State Circuits, Vol. 23, No. 5, October 1988, pp. 1218˜1223.

Charge pump circuit reducing noise and charge error and PLL circuit using the same


A driver assembly with an efficient mechanism for transferring heat away from an integrated circuit (IC) chip via a heat transfer member and conductive pattern lines formed on a substrate. The IC chip is mounted on connectors and is placed above the substrate. The IC chip operatively communicates with the display panel via at least a subset of the conductive pattern lines and a subset of the connectors. A heat transfer member is formed on the substrate and is configured to transfer heat generated by the integrated circuit to a component having a lower temperature than the IC chip. A heat transfer element is placed between the IC chip and the heat transfer member to transfer the heat generated by the IC chip to the heat transfer member.

1. Field of the Disclosure
This disclosure relates to transferring heat generated by an integrated circuit (IC) chip of a driver assembly for supplying operating signals to a display device to prevent overheating of the IC chip.
2. Description of the Related Art
Display devices are used for displaying information on a display panel for visual interaction with users. Various types of display technologies were developed and currently available for use in electronic devices. The display devices may incorporate various types of technology including, among others, liquid crystal display (LCD) technology, organic light emitting display (OLED) technology, electrophoretic display technology, field emission display (FED) technology, and plasma display technology. In general, display devices include a display panel and a driver assembly for providing signals to operate pixel elements in the display panel.
One conventional way of implementing the driver assembly is by using chip-on-film (COF) technology. The COF generally uses a film (e.g., flexible substrate) and a driver integrated circuit (IC) chip mounted on the film. Wiring patterns are formed on the film and bumps are placed between the driver IC and the film to connect the driver IC to the wiring patterns. The wiring patterns connect the IC chip to signal lines of a display panel.
As the size of the display panel increases, the operating frequency and the operating voltage of the driver IC chip also increases. The increased frequency and the operating voltage of the driver IC increases the heat generated within the driver IC. Such increase the internal heat generation can cause the driver IC to overheat, resulting in malfunctioning as well as damage to the driver IC chip. The heating of the driver IC chip can compromise the reliability of the display device.


A saddle 18 is movable along a guide means 16 provided, passing through an neighborhood of machining area MA of a plurality of machine tools 1, 2. The saddle 18 is provided with a machining head 33, being free to selectively insert in and retreat from the machining area MA, and a plurality of kinds of nozzles 48 for ejecting laser beam. The nozzle 48 suitable for a portion of workpiece 3, 4 to be hardened is selected so as to attach it to the machining head 33. When hardening is instructed, the nozzle 48 is moved to a desired position with respect to the workpiece 3, 4 in the state of the workpiece 3, 4 located on the machine tool 1, 2, and the laser beam 51 is ejected from the nozzle 48 so as to harden the workpiece 3, 4.

This invention relates to a laser beam hardening device for hardening a part of a workpiece, and in particular, relates to a laser beam hardening device suitable for hardening a workpiece on a machine tool.
As a device for partially hardening a workpiece, there is a laser beam hardening device. Wide experience is necessary for setting working conditions, such as setting the shape of a workpiece, setting the portion or bounds of workpeice to be hardened or their working methods since the direction of laser beam irradiated from a machining head is constant in a conventional laser beam hardening device.
When workpieces to be hardened with laser beam should be produced in large quantities, it is sufficient to provide an exclusive laser beam hardening device for only such workpieces. Thereby workpieces having constant quality can be machined without depending on a worker""s experience. When many kinds of workpieces should be produced in small quantities (especially, when one article should be produced), it is impossible to provide a laser beam hardening device exclusive for the workpiece for economical reasons.
Besides, concerning a workpiece requiring high accuracy, after-routine owing to heat indication at the time of hardening, such as re-polishing may be necessary. In this case, a workpiece taken out of a machine tool should be attached to the machine tool again after hardening so as to machine. At the result, the work for hardening routine takes longer time. And, machining accuracy may be decreased owing to the dispersion of reproducibility of a position when a workpiece is attached to a machine tool. The object of the present invention is to provide a laser beam hardening device capable of improving productivity of workpieces without a specific skill, having shorter time for hardening routine, taking the above-mentioned circumstances into consideration.
The present invention is laser beam hardening device, comprising a guide means provided passing through a neighborhood of machining area of a plurality of machine tools having a saddle provided at said guide means, being free to move along said guide means.
The laser beam hardening device further comprises a machining head provided at said saddle, being free to selectively insert in and retreat from said machining area of a plurality of said machine tools and a nozzle attachably and detachably provided at said machining head, being capable of ejecting laser beam.
Additionally, the laser beam hardening device comprises a nozzle holder capable of attachably and detachably holding said nozzles and a nozzle exchanging means for exchanging said nozzle between said machining head and said nozzle holder.
Hardening can be performed in such a manner that the machining head of the laser beam hardening device, installing the nozzle fitting for the portion of a workpiece to be hardened, is moved to a workpiece located at the machining area of each machine tool. Laser beam is exposed to a necessary portion of the workpiece; thereby hardening is possible without specific skill. Even in the case where after-routine due to heat indication at the time of hardening, such as polishing, is necessary, the after-routine can be immediately performed since the workpiece is set on the machine tool. Then, the machining accuracy does not decrease since it is not necessary to attach a wokpiece to the prior place of a machine tool again. Thus the attaching place of the workpiece does not vary.
Besides, the time for hardening routine can be shortened so as to improve the productivity of a workpiece. And, continuous hardening work is possible concerning a plurality of machine tools with one laser beam hardening device since the machining head is free to selectively insert in and retreat from the machining area of a plurality of machine tools. Thus it""s working efficiency is high.
The laser beam hardening device may have a guide means, passing through an upper area of said machining area of a plurality of said machine tools.
Accordingly, the guide means is not an obstruction when a workpiece is carried in and carried out of each machine tool and machine tools are maintained, in addition to the effects of the invention.
The laser beam hardening device may also have nozzle exchanging means having a driving means for driving said nozzle holder and said machining head being free to relatively close to and apart from each other.
Furthermore the freedom degree concerning the position of the machining head increases and the workpiece having complex shape can be dealt with, in addition to the effects of the invention.
The laser beam hardening device may also have a nozzle holder that can be moved along said guide means together with said saddle.
Accordingly, it is not necessary to move the saddle along the guide means when the nozzle is exchanged, and the nozzle can be exchanged in a short time so as to improve workability, in addition to the effects of the invention.
The laser beam hardening device may also have a nozzle exchanging means, which has a magazine providing a plurality of said nozzle holders. The plurality of nozzles can be exchanged in a short time, and then workability can be improved, in addition to the effects of the invention.
The laser beam hardening device may also have a plurality of said nozzles, and an optical path having different form of ejecting laser beam is formed at each nozzle.
Accordingly, a plurality of nozzles suitable for the part to be hardened of the workpiece, which is an object of hardening work, can be located, and the workpiece having more complex shape can be also dealt with, in addition to the effects of the invention.


A system and method for communicating a vehicle with a calling party are disclosed in which even when a communication circuit is interrupted during a data communication of the system with the calling party such as a base station due to a worse circuit condition, the calling from the system to the calling party is carried out without operation of a switch for activating the system to start calling so that the communication with the calling party is restarted. The communication data includes a vehicle identification code (ID information) and/or instantaneous position of the vehicle.

(1) Field of the Invention
The present invention relates to a system and method for communicating a vehicle with a calling party, e.g., a base station, particularily but not exclusively suitable for informing the base station of a location of the vehicle in which the system is mounted.
(2) Background of the Art
Recently, many automotive vehicles have adopted, so called, (hand-free) automotive telephones as vehicle communication systems.
Such kinds of vehicular communication systems are exemplified by Japanese Patent Application First (Nonexamined) Publications sho 50-75706 published on June 21, 1976, sho 58-161100 published on Sept. 24, 1983, and sho 60-100715 published on June 4, 1985.
Furthermore, a Japanese Utility Model Application No. sho 61-164614 filed on Oct. 27, 1986 exemplifies one of the other vehicular communication systems which informs the base station of the instantanous location of the vehicle in which the communication system is mounted.
In the above-identified Japanese Utility Model Application, when a corresponding switch installed on a transceiver is turned on, a positional information and identification number allocated to the vehicle are transmitted to the base station, the positional information being derived from means, installed on the vehicle, for detecting a position of the vehicle.
The vehicular communication system disclosed in the above-identified Japanese Utility Model Application has a feature capable of informing the position of the vehicle in which the system is mounted to the base station according to its necessity.
However, when in the automotive telephones, the communications are carried out during the movement of the vehicle on roads, a circuit interruption occurs when the vehicle passes through tunnels or underpasses or otherwise when a circuit condition is worse. In this case, a redialing becomes necessary.
In addition, in the previously proposed vehicular communication system, a communication circuit for the automotive vehicles is used to inform the vehicular position to the base station. Therefore, when the circuit interruption occurs, the operator (usually the vehicle driver) confirms the occurrence of the circuit interruption and a manual operation is needed to cause the system to be activated. This follows that a speedy activation cannot be carried out in case of emergency and, in worst cases, the vehicular position cannot be informed to the base station in the case when no reoperation is possible.

System and method for communicating a vehicle with a calling party


A material-conveying system comprising a conveyor for conveying material to a bin and a conveyor positioning system associated with the conveyor. The conveyor positioning system comprises a processor for positioning the conveyor relative to the bin. The conveyor comprises a spout and the bin comprises an opening. The conveyor positioning system positions the spout of the conveyor over the opening of the bin. The conveyor positioning system in one implementation comprises a Global Navigation Satellite System-Real Time Kinematic (GNSS-RTK) positioning system that includes a fixed base station and a GNSS receiver on the conveyor.

In the agricultural industry, conveyors or material-conveying systems are used to load grain, seed, fertilizer or other such bulk materials into a storage bin or to offload product from a storage bin.
Aligning a conveyor with a bin, particularly aligning a spout of the conveyor with a bin opening, is difficult and time-consuming and often requires two persons (a spotter and a driver) to perform the alignment. A system to position a conveyor relative to a bin is therefore highly desirable.


Humanized antibody to a pathologically mislocated form of N-cadherin detects and eliminates cells that express the protein extracellularly. These cells are found in fibrotic conditions within heart, lung, and liver, as well as kidney, skin, and other organs effected by fibrosis. The antibody does not affect cells with normal, subcellular location of the protein.

Fibrosis is the aberrant remodeling of tissue architecture which results in loss of function and inevitably organ failure. It can arise in any organ in the body and manifest from many different disease origins; it is the major and only predictable gross physiological feature of many different diseases that is linearly correlated to organ failure. It is a biologically conserved process regardless of the organ of origin and common endpoint regardless of insult [1]. In the United States, 45% of all deaths can be attributed to some kind of chronic fibrotic related disease [2, 3]. Collectively, fibrotic disease kills more people than cancer. The current scientific theory describes fibrosis as the pathological and constitutive activation state of fibroblasts which result in excessive extracellular matrix turnover and deposition that interferes with normal organ function. Currently, an activated state of these fibroblasts is defined by their acquisition of alpha-smooth muscle actin (α-SMA) protein. Fibroblasts expressing this protein are defined as myofibroblasts, which are an extremely active, synthetic, tissue remodeling cell type. However, a true disease specific marker for these cells does not currently exist.
There is a continuing need in the art to detect and eliminate pathological cells involved in fibrosis.

This patent is subject to a terminal disclaimer.

Anti-pro-N-cadherin antibodies and methods of treating pathological fibrotic conditions and tumor cells


An artificial heart with a centrifugal pump is disclosed. In one embodiment, the artificial heart includes an impeller disposed in a housing. The impeller is configured to rotate to circulate blood through the housing. The impeller may include a set of blades on a first side of the impeller and a set of vanes on a second side opposite the first. The blades on the first side and the vanes on the second side allow blood circulation from both the first and the second sides of the impeller. The artificial heart may also or instead include a diffuser with adjustable vanes that enable variation in the output characteristics of the artificial heart pump. Various other artificial hearts, pumps, systems, and methods, including control systems and methods, are also disclosed.

This section is intended to introduce the reader to various aspects of art that may be related to various aspects of the presently described embodiments. This discussion is believed to be helpful in providing the reader with background information to facilitate a better understanding of the various aspects of the present embodiments. Accordingly, it should be understood that these statements are to be read in this light, and not as admissions of prior art.
The human body, like that of other animals, depends on oxygen for survival. Humans and many other animals have circulatory systems for delivering oxygen (among other things) to cells in the body. Taking the human body as an example, the human heart pumps oxygenated blood through blood vessels to the cells. As may be appreciated, natural human hearts typically enable both pulmonary circulation (generally, the flow of blood to and from the lungs to allow oxygenation of the blood) and systemic circulation (generally, the delivery of oxygen-rich blood to and return of oxygen-poor blood from cells) by pumping the blood through blood vessels with repeated contractions.
But like many other organs, the heart is susceptible to disease and failure. In some instances, a patient may be diagnosed with a heart defect so severe that a new heart is the recommended treatment. While transplants of natural hearts have been performed for decades, such a procedure requires a suitable donor heart. And patients waiting for new hearts greatly outnumber suitable donors. Artificial hearts may be used to sustain patient life, whether serving as a permanent replacement or as a bridge to a later heart transplant. Artificial hearts may include a centrifugal pump that drives the blood through a patient's circulatory system. Given the physiological importance of the circulatory system, improvements in artificial heart technology may directly lead to improved patient outcomes and quality of life.


Disclosed herein are methods and sequences to preferentially suppress the expression of the mutated huntingtin (“htt”) protein over expression of the normal htt protein. Also disclosed are methods comprising screening an individual for the heterozygous presence of one or more single nucleotide polymorphisms within the individual's Huntington's genes; administering nucleic acid molecules comprising nucleotide sequences that preferentially suppress the expression of amino acid sequences encoding for mutated huntingtin (“htt”) over suppressing the expression of amino acid sequences encoding for normal htt by targeting an area of a Huntington's disease gene that is heterozygous for the presence of one or more single nucleotide polymorphisms.

Huntington's disease ("HD") is a degenerative brain disorder. It slowly destroys an affected individual's ability to walk, think, talk and reason. Symptoms include changes in cognitive ability, such as impaired short-term memory and a decreased ability to concentrate; changes in mood, such as the development of mood swings, depression and irritability; and changes in coordination and physical movement such as clumsiness, involuntary movements and twitching. These symptoms gradually worsen until HD patients die, approximately 15-20 years after the onset of the disease.
While the biochemical cause of HD is not yet fully understood, it is now known that HD is inherited. Organisms typically inherit two copies of each gene, one from each parent. An individual copy of a gene inherited from one parent is called an allele. With regard to the inheritance of HD, every individual who inherits a HD-causing allele from either parent will develop the disease.
One breakthrough in research regarding HD has been the identification of the mutated gene that causes HD. Based on this breakthrough, researchers and physicians now can predict which individuals will develop HD. Specifically, researchers and physicians can predict which individuals will develop HD by counting the number of "CAG repeats" that exist within an individual's HD genes. If a person has 35 or less CAG repeats in each of their HD gene alleles, that person will not develop HD. If a person has more than 35 CAG repeats in either of their HD gene alleles, that person will develop the disease. The more CAG repeats a person has over 35 in either gene allele, the earlier the person will develop the symptoms of HD.
The HD gene encodes for a protein called "huntingtin" ("hit"). The exact function of htt is not known. However, it is known that the increased number of CAG repeats in HD-causing gene alleles leads to htt proteins with expanded polyglutamine sequences. Expanded polyglutamine sequences in proteins confer novel toxic properties resulting from a tendency of the protein to misfold and form aggregates within brain cells. Thus, suppressing the production of htt in brain cells may provide an avenue to prevent the accumulation of toxic htt in brain cells. This prevention can provide an avenue to further study the physiological mechanisms underlying HD and may also prevent or alleviate the symptoms or occurrence of HD.
While suppressing the production of htt could provide a method to prevent or treat the symptoms of HD, because its functions are not fully understood, fully blocking the expression of this protein may not be desirable. Indeed, animal studies have shown that htt is critical at least during development because animals lacking the protein altogether do not survive. Thus, it would be desirable to preferentially suppress the expression of toxic or mutated htt encoded for by a mutated HD allele while allowing expression of the normal HD allele that encodes for a normal htt protein.
Recent developments in genetic technologies have made the selective suppression of certain alleles and proteins, such as the mutated HD gene allele and the mutated htt protein, possible. Some background in the art is required to understand the potential impact of these technologies. Generally, for a protein to exert an effect, the cell that will use the protein must create it. To create a protein the cell first makes a copy of the protein's gene sequence in the nucleus of the cell. This copy of the gene sequence that encodes for the protein (called messenger RNA ("mRNA")) leaves the nucleus and is trafficked to a region of the cell containing ribosomes. Ribosomes read the sequence of the mRNA and create the protein for which it encodes. This process of new protein synthesis is known as translation. A variety of factors affect the rate and efficiency of protein translation. Among the most significant of these factors is the intrinsic stability of the mRNA itself. If the mRNA is degraded quickly within the cell (such as before it reaches a ribosome), it is unable to serve as a template for new protein translation, thus reducing the cell's ability to create the protein for which it encoded.
Based on the foregoing, the technology of RNA interference ("RNAi") has emerged. RNA interference is, in fact, a naturally occurring mechanism for suppressing gene expression and subsequent protein translation. RNA interference suppresses protein translation by either degrading the mRNA before it can be translated or by binding the mRNA and directly preventing its translation. Generally, RNAi has been used to suppress the expression of both gene alleles that lead to the production of a given protein. However, in some cases, such as those involved in the present invention, it is desirable to suppress the expression of only one allele.
Recently, several single nucleotide polymorphisms ("SNPs") have been identified that can be used to distinguish between the two HD gene alleles in human cells. SNPs are single nucleotide changes in the nucleotide sequence of a given gene. Thus, using RNAi, it is now possible to derive therapeutic agents to specifically suppress the expression of a mutated HD gene allele carrying a SNP. This personal approach can lead to individualized or "directed" therapeutics for HD patients, and provides an avenue to suppress the expression and actions of mutated toxic htt in an attempt to prevent or alleviate the symptoms of HD.

Methods and sequences to preferentially suppress expression of mutated huntingtin


An apparatus for carrying out inductively coupled plasma mass spectrometry to effect identification and quantification of a trace element contained in a sample solution. A plasma torch is provided for converting the sample solution into a plasma. A sampling interface has a sampling orifice and a skimmer orifice for drawing therethrough the plasma to form an ion beam. A mass filter is provided for effecting mass-separation of the ion beam to filter ions. A detector detects ions which pass through the mass filter. An optical system is composed of a lens, a deflector and a junction member for efficiently introducing the ion beam from the sampling interface into the mass filter. An ammeter is connected to the junction member between the optical system and the mass filter. A monitoring device is provided for monitoring the state of the ion beam within the optical system according to the output of the ammeter and an adjusting device is provided for adjusting the optical system while monitoring the output of the ammeter and an output of the detector.

The present invention relates to a high frequency or radio frequency inductively coupled plasma mass spectrometry apparatus (hereinafter, referred to as "ICP-MS") for carrying out analysis of a trace element contained in a sample solution.
ICP-MS apparatus typical of the prior art, as shown in FIG. 2, is comprised of a plasma torch 1 for producing a plasma 2, a sampling orifice 3 which has a small opening diameter, a skimmer orifice 4 having a small opening diameter for passing an ion beam 5, a lens 6, a deflector 7, a junction member 8c, a mass filter 9, a detector 10, a power supply 11 for powering an optical system, an I/0 interface 12, a computer 13, and a display device 14.
A sample solution (not shown) is fed to the plasma torch 1 together with a carrier gas such as argon to form the plasma 2, which is injected through the sampling orifice 3. A sampling interface is formed by the sampling orifice 3, the skimmer orifice 4 and a vacuum region between orifices 3 and 4. A vacuum is created in the latter region by a suitable vacuum device (not shown).
Plasma torch 1 emits plasma 2 toward sampling orifice 3 and this plasma travels along a path having an introduction axis which extends through, and is centered in, orifices 3 and 4. The plasma 2 passes through the sampling interface to form the ion beam 5.
The optical system is composed of lens 6 having an optical axis aligned with the above-mentioned introduction axis, deflector 7 and junction member 8c and functions to introduce the ion beam 5 efficiently to mass filter 9 while blocking light emitted from plasma 2. Namely, deflector 7 deflects ion beam 5 from the introduction axis of plasma torch 1, the sampling interface and the lens 6 to a laterally offset exit axis defined by a passage in junction 8c and mass filter 9 so as to block light, which travels along linear paths, from reaching mass filter 9. At the same time, lens 6 operates to focus ion beam 5 onto an inlet of mass filter 9, which inlet is defined by the passage in junction member 8c.
The ion beam 5 which enters mass filter 9 contains various ion species and a given ion species having a particular mass specified by computer 13 can reach an outlet of the mass filter, while other ion species will be diverted in mass filter 9. The ion species passing through mass filter 9 is detected by detector 10 and the detected ions are counted. The counting result is fed through I/0 interface 12 to computer 13.
Computer 13 operates to identify a particular trace element within the sample solution and to calculate the concentration thereof according to the counting result from detector 10 and the mass information fed to mass filter 9. The identification and calculation results are indicated in display device 14.
The mass filter is normally composed of a quadrupole mass spectrometer, and the detector is composed of a channeltron. The optical system, mass filter 9 and detector 10 are disposed within a high vacuum space evacuated by a vacuum pump (not shown). Adjustment of the lens 6 and deflector 7 is manually carried out by the operator, together with regulating of power supply 11 for the optical system while monitoring the output level of detector 10.
In the conventional apparatus, as described above, adjustment of the optical system is effected manually based solely on the output signal from detector 10. This has given rise to various problems. For example, adjustment is extremely time-consuming and complicated, especially when the operator is not fully familiar with the structure and features of the optical system. Moreover, the results of the quantity analysis may not be reliable, especially in the lower critical range of the detector, when the solution analysis is undertaken with incomplete adjustments.

Inductively coupled plasma mass spectrometry apparatus