CN101395206B - Silicone elastomer gels - Google Patents

Silicone elastomer gels Download PDF

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CN101395206B
CN101395206B CN200780007575.4A CN200780007575A CN101395206B CN 101395206 B CN101395206 B CN 101395206B CN 200780007575 A CN200780007575 A CN 200780007575A CN 101395206 B CN101395206 B CN 101395206B
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sio
sih
composition
component
silicone elastomer
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CN101395206A (en
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S·林
J·麦克维
P·范多特
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Dow Silicones Corp
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Dow Corning Corp
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Abstract

Gel compositions are disclosed containing a silicone organic elastomer from the reaction of an organohydrogensiloxane having at least two SiH containing cyclosiloxane rings in its molecule, a compound or mixture of compounds having at least two aliphatic unsaturated groups in its molecule, and a hydrosilylation catalyst. The silicone elastomer reaction product may itself be a gelled composition, or optionally may be contained in a carrier fluid to form a gel. The gel compositions may further contain a personal or healthcare active.

Description

Silicone elastomer gels
The cross reference of related application
According to 35U.S.C. § 119 (e), the application requires the rights and interests of the U.S. Patent application 60/784340 of submitting on March 21st, 2006 and the U.S. Patent application 60/838803 of submitting on August 18th, 2006.
Technical field
The present invention relates to gelatinous composition, it comprises by have two compound or the mixture of compound and silicone elastomers that the hydrosilylation catalysts reaction obtains that contain the organic radical hydrogen siloxane of the cyclosiloxane ring of SiH, have two aliphatic unsaturated hydrocarbon bases in its molecule in its molecule at least at least.This silicone elastomer reaction product itself can be the composition of gelling, perhaps optionally is included in and forms gel in the carrier fluid.This gelatinous composition can further contain a guy or health care activeconstituents.Can activeconstituents be incorporated in the gel by preload or back loading method.
Background technology
Silicone elastomer is widely used in the personal care application because of its unique silk quality and powdery sensation.But the organic solvent of these elastomerics gelling volatility organosilicon fluids of great majority and low polarity, for example Permethyl 99A..In United States Patent (USP) 5880210 and US5760116, instructed the representative example of this silicone elastomer.In order to improve the consistency of silicone elastomer and various personal care compositions, alkyl, polyethers, amine or other organo-functional groups are grafted on the silicone elastomer main chain.In US5811487, US5880210, US6200581, US5236986, US6331604, US6262170, US6531540 and US6365670, instructed the representative of the silicone elastomer of this organic functional.Many these silicone elastomers have limited consistency to various personal care compositions, personal care activeconstituents and health care activeconstituents.In the presence of personal care composition, personal care activeconstituents and health care activeconstituents, these elastomericss have lost thickening and gelation efficiency and even sense organ advantage.Require further improvement the consistency of silicone elastomer and various personal care composition and activeconstituents.
Yet, still need further to improve for example organosilyl efficient of volatility of gelling volatility cosmetic fluid by silicone elastomer, and especially by adding silicone elastomer in volatility cosmetic fluid, improve the rheology thickening effectiveness.In addition, also seek the additional advantage of the composition of gelling, for example improve transparency and/or the improved aesthetic feeling when being applied on the skin of the silicon composition of gelling.
The contriver finds, and the silicone elastomer of being derived by ring-type organic radical hydrogen siloxane provides the composition of gelling effectively.The composition of gained gelling also has extra advantage, for example improved aesthetic feeling and with personal care composition and the improved consistency of activeconstituents.
Summary of the invention
Disclosure of the present invention relates to a kind of gelatinous composition, and it comprises the silicone elastomer that is obtained by the following substances reaction:
A) in its molecule, have at least two organic radical hydrogen siloxanes that contain the cyclosiloxane ring of SiH,
B) in its molecule, have the compound of at least two aliphatic unsaturated hydrocarbon bases or the mixture of compound,
C) hydrosilylation catalysts, and
D) optional carrier fluid.
Disclosure of the present invention further relates to the method that preparation contains the silicone elastomer gels of activeconstituents, and the method comprises:
I) make the following substances reaction:
A) have the organic radical hydrogen cyclosiloxane of at least two SiH unit at the siloxanes ring,
B) in its molecule, have the compound of at least two aliphatic unsaturated hydrocarbon bases or the mixture of compound,
C) hydrosilylation catalysts
Form:
A) in its molecule, have at least two organic radical hydrogen siloxanes that contain the cyclosiloxane ring of SiH,
The molar ratio range of the aliphatic unsaturated group SiH unit and the B component of component in a) wherein) is 2/1-8/1,
II) at D) optional carrier fluid and E) in the presence of personal care or the health care activeconstituents, further make:
A) in its molecule, have the organic radical hydrogen siloxane of the cyclosiloxane ring that contains at least two SiH, with extra consumption
B) in its molecule, have the compound of at least two aliphatic unsaturated groups or the mixture of compound,
C) hydrosilylation catalysts
Reaction forms silicone elastomer gels.
Can be by in the process that forms the organosilicon organic elastomer gels, making personal care or health care activeconstituents have (preload method), perhaps by mixing personal care or health care activeconstituents and formed organosilicon organic elastomer gels (back loading method), it is incorporated in the organosilicon organic elastomer gels.
Describe in detail
(A) has the organic radical hydrogen siloxane of the cyclosiloxane ring that contains at least two SiH
Component of the present invention (A) is to have at least two organic radical hydrogen siloxanes that contain the cyclosiloxane ring of SiH in its molecule.In the present invention, be suitable for as component A) the organic radical hydrogen siloxane be any organopolysiloxane that in its molecule, has at least two cyclosiloxane rings and have hydrogen (SiH) unit of at least one and silicon bonding at each siloxanes ring.Organopolysiloxane is well-known in the art, and usually is expressed as and comprises any amount of (R 3SiO 0.5), (R 2SiO), (RSiO 1.5) or (SiO 2) siloxy units, wherein R is any organic group independently.If R is methyl in the siloxy units formula of organopolysiloxane, then corresponding siloxy units usually is expressed as M, D, T or Q siloxy units.The cyclosiloxane ring contains at least three siloxy units (that is in order to form the required minimum value of siloxanes ring), and can be (the R that forms ring structure 3SiO 0.5), (R 2SiO), (RSiO 1.5) or (SiO 2) any combination of siloxy units, condition is that at least one the ring siloxy units on each siloxanes ring contains a SiH unit, that is in ring at least one (R of existence 2HSiO 0.5), (RHSiO) or (HSiO 1.5) siloxy units.These siloxy units can be expressed as respectively M H, D HAnd T HSiloxy units, wherein R is methyl.
A) organic or siloxanes or its combination are joined together the cyclosiloxane ring in the organic radical hydrogen siloxane by divalence.Divalent linker can be expressed as Y and cyclosiloxane can be expressed as G.Therefore, organic radical hydrogen siloxane of the present invention can be used general formula G-[Y-G] aExpression, wherein G is above-described cyclosiloxane, and Y is divalent organic group, siloxanes, polyoxy alkylidene or its combination, and subscript a is greater than 0.
If Y is divalent organic group, then it can be to contain the conduct aliphatic series of 1-30 carbon or the bivalent hydrocarbon radical of aromatic structure, and can branching or nonbranched.Perhaps, Y contains 2-20 carbon, perhaps contains the alkylidene group of 4-12 carbon.
If Y is divalent organic group, then it is also optional from organic polymer, for example polyoxy alkylidene.
If Y is siloxanes, then its optional self-contained at least two bivalent hydrocarbon radical (is used R 1Expression) any organopolysiloxane.Therefore, siloxanes connection base can be to contain at least two average formula R of usefulness 1R mSiO (4-m)/2Any organopolysiloxane of the siloxane unit of expression:
Wherein R is organic group,
R 1Bivalent hydrocarbon radical, and
M is 0-3.
R 1Base may reside on intramolecular any single, two or three siloxy units of organopolysiloxane, for example is present in (R 1R 2SiO 0.5), (R 1RSiO) or (R 1SiO 1.5) and in conjunction with not containing R 1Substituent other siloxy units are (R for example 3SiO 0.5), (R 2SiO), (RSiO 1.5) or (SiO 2) on the siloxy units, wherein R is any organic group independently, condition is to have at least two R in organopolysiloxane 1Substituting group.Representative R 1Base comprises ethylidene, propylidene, butylidene, isobutylidene, hexylidene and similar homologue.Perhaps, R 1It is ethylidene.
Be suitable for comprising as the representative non-limiting example of the basic this siloxane based structure of siloxanes connection:
(R 2R 1SiO 0.5)(R 2SiO) x(R 2R 1SiO 0.5)
(R 3SiO 0.5)(R 2SiO) x(R 1RSiO) y(R 3SiO 0.5)
(R 3SiO 0.5)(R 2SiO) x(R 1RSiO) y(RSiO 1.5) z(R 3SiO 0.5)
X 〉=0 wherein, y 〉=2 and z 〉=0.
Can be by the hydrosilylation reactions of following substances, preparation has at least two organic radical hydrogen siloxanes (component A) that contain the cyclosiloxane ring of SiH:
A) have the organic radical hydrogen cyclosiloxane of at least two SiH unit at the siloxanes ring,
B) in its molecule, have the compound of at least two aliphatic unsaturated groups or the mixture of compound.
The organic radical hydrogen cyclosiloxane (a) that has at least two SiH unit at the siloxanes ring can contain any amount of siloxy units (as defined above), and condition is to have at least two SiH unit at the cyclosiloxane ring.For example, cyclosiloxane can comprise any amount of M, M H, D, D HOr T HSiloxy units.The general formula of representative non-limiting example that can be used for preparing this organic radical hydrogen cyclosiloxane of component (A) is D H aD b, a 〉=1 and b 〉=0 and a+b 〉=3 wherein.Perhaps, the optional self-drifting of organic radical hydrogen cyclosiloxane is [(CH 3) HSiO] gThose, wherein g is 3-8, for example D H 4, D H 5, D H 6, or its mixture.
Be described as B component include the suitable combination thing of at least two aliphatic unsaturated hydrocarbon bases at its molecule below).
The hydrosilylation reactions that relates to organic radical hydrogen siloxane and unsaturated compound is well-known.Can use any suitable hydrosilylation catalysts known in the art, perhaps it can be selected from the following component C that is described as) those.Any known hydrosilylation technology and reaction can be used for by i) have the organic radical hydrogen cyclosiloxane of at least two SiH unit and B at the siloxanes ring) in its molecule, have the compound of at least two aliphatic unsaturated groups or the mixture of compound prepares component A).Yet, carry out this reaction, its mode is so that be provided at and have at least two organic radical hydrogen siloxanes that contain the cyclosiloxane ring of SiH in its molecule.
Therefore, the every a part of component A of the present invention contains at least two hydrogen atoms with the silicon bonding, and perhaps every a part contains at least four hydrogen atoms with the silicon bonding, and perhaps every a part contains at least six hydrogen atoms with the silicon bonding.This can be by realizing at the organic radical hydrogen cyclosiloxane that a) has two SiH unit at the siloxanes ring that uses for the compound that contains two aliphatic unsaturated groups at its molecule molar excess in the hydrosilylation reactions at least at least.Molar excess can be expressed as the mol ratio of SiH unit and unsaturated group, and this proportional range can be 2/1-8/1, perhaps 2/1-6/1, perhaps 3/1-4/1.
Perhaps, can be used as component A) the optional comfortable WO03/093349 of organic radical hydrogen siloxane in any organic radical hydrogen siloxane of instructing, at this by with reference to the instruction of introducing about suitable organic radical hydrogen siloxane.
Can be used as in the present invention component A) the viscosity of organic radical hydrogen siloxane typically be 5-50,000mPas, perhaps 10-10,000mPas, perhaps 25-2,000mPas.
Component A) representative non-limiting example comprises:
Figure G2007800075754D00061
The additive that is called inhibitor or stablizer can join component A) in.In order to stablize component A) purpose, can be in storage process, perhaps adding B component) before the preparation silicone elastomer gels, add inhibitor, for example at described in the WO03/093369 those.Inhibitor is optional from known any compound with inhibition platinum base hydrosilylation reactions effect.The example of known inhibitor comprises triphenylphosphate, tocopherol (vitamin-E) and Yoshinox BHT.Especially preferred inhibitor is Vitamin A Palmitate 1.7 M.I.U/Gram, or VAP.When using VAP, typically its addition is with respect to per 100 parts of component A) be 0.05-2.0 part.
(B) in its molecule, have the compound of at least two aliphatic unsaturated hydrocarbon bases or the mixture of compound
Component (B) is to contain the compound of at least two aliphatic unsaturated groups or the mixture of compound at its molecule.This compound can be any diene, diine or alkene-alkine compounds.Diene, diine or alkene-alkine compounds are those compounds (comprising polymkeric substance), wherein have at least two aliphatic unsaturated groups and have certain intervals between intramolecular these groups.Typically, described unsaturated group is in the end of this compound, if perhaps the part of polymkeric substance is then hung Ji Chu in side.The compound that contains end or side extension unsaturated group can be used general formula R 2-Y-R 2Expression, wherein R 2Be the unit price unsaturated aliphatic alkyl that contains 2-12 carbon atom, and Y is divalent organic group or siloxanes or these combination.Typically, R 2CH 2=CH-, CH 2=CHCH 2-, CH 2=CH (CH 2) 4-, CH 2=C (CH 3) CH 2-or CH ≡ C-, and similarly replace unsaturated group, for example H 2C=C (CH 3)-and HC ≡ C (CH 3)-.
As B component) general formula be R 2-Y-R 2Compound can be considered " organic ", " hydrocarbon ", " organic polymer ", " polyethers " or " siloxanes " or its combination, this depends on the selection of Y.Y can be divalence hydrocarbon, siloxanes, polyoxy alkylidene, polyalkylene, poly-inferior iso-alkyl, hydrocarbon-silicone copolymers or its mixture.
In one embodiment, to be selected from general formula be R to component (B) 2-Y 1-R 2Organic compound, be expressed as (B herein 1), R wherein 2The unit price unsaturated aliphatic group that contains 2-12 carbon atom, and Y 1It is bivalent hydrocarbon radical.Bivalent hydrocarbon radical Y 1Can contain 1-30 carbon, as or aliphatic series or aromatic structure, and can be branching or nonbranched.Perhaps, at B 1Interior connection base Y 1It can be the alkylidene group that contains 1-12 carbon.Component (B 1) optional α from containing 1-30 carbon, ω-unsaturated chain alkene or alkynes, and composition thereof.Component (B 1) can exemplify but be not limited to 1,4-pentadiene, 1,5-hexadiene, 1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, 1,11-12 carbon diene, 1,13-14 carbon diene and 1,19-20 carbon diene, 1,3-diacetylene, 1,5-hexadiyne (dipropargyl) and 1-hexene-5-alkynes.
In another embodiment, component (B) is selected from R 2-Y 2-R 2Compound is expressed as (B herein 2), Y wherein 2It is siloxanes.Y 2Siloxanes can be selected from and be bonded at least two organic groups with aliphatic unsaturated link(age) and (be expressed as R 2) go up and formation R 2-Y 2-R 2Any organopolysiloxane of structure.Therefore, component (B 2) can be to contain with average formula R 2R mSiO (4-m)/2Any organopolysiloxane of at least two siloxane units of expression and composition thereof:
Wherein R is organic group,
R 2The unit price unsaturated aliphatic group of above definition, and
M is 0-3.
R 2Base can be present on intramolecular any single, two or three siloxy units of organopolysiloxane, for example is present in (R 2R 2SiO 0.5), (R 2RSiO) or (R 2SiO 1.5) and in conjunction with not containing R 2Substituent other siloxy units are (R for example 3SiO 0.5), (R 2SiO), (RSiO 1.5) or (SiO 2) on the siloxy units, wherein R is any organic group independently, perhaps contains the alkyl of 1-30 carbon, perhaps contains the alkyl of 1-30 carbon, perhaps methyl, condition is to have at least two R in organopolysiloxane 2Substituting group.
Be suitable for as component (B 2) this siloxanes R 2-Y 2-R 2The representative non-limiting example of structure comprises:
(R 2R 2SiO 0.5)(SiO 2) w(R 2R 2SiO 0.5)
(R 2R 2SiO 0.5)(SiO 2) w(R 2SiO) x(R 2R 2SiO 0.5)
(R 2R 2SiO 0.5)(R 2SiO) x(R 2R 2SiO 0.5)
(R 3SiO 0.5)(R 2SiO) x(R 2RSiO) y(R 3SiO 0.5)
(R 3SiO 0.5)(R 2SiO) x(R 2RSiO) y(RSiO 1.5) z(R 3SiO 0.5)
(R 3SiO 0.5)(R 2SiO) x(R 2RSiO) y(SiO 2) w(R 3SiO 0.5)
W 〉=0 wherein, x 〉=0, y 〉=2 and z 〉=0, R is organic group, and
R 2It is unit price unsaturated aliphatic alkyl.
B 2Can be selected from the polydimethylsiloxane (vinylsiloxane) of vinyl functional or the polydimethylsiloxane (hexenyl siloxanes) of hexenyl official energy, for example have those of following average formula:
CH 2=CH(Me) 2SiO[Me 2SiO] xSi(Me) 2CH=CH 2
CH 2=CH(CH 2) 4-(Me) 2SiO[Me 2SiO] xSi(Me) 2-(CH 2) 4-CH=CH 2
Me 3SiO[(Me) 2SiO] x[CH 2=CH(Me)SiO] ySiMe 3
Wherein Me is methyl, x 〉=0, and perhaps x is 0-200, perhaps x is 10-150,
Y 〉=2, perhaps y is 2-50, perhaps y is 2-10.
The polydimethylsiloxane of vinyl functional is known, and many commercially available.
In another embodiment, to be selected from general formula be R to component (B) 2-Y 3-R 2Polyether compound, be expressed as (B herein 3), R wherein 2As defined above, and Y 3That general formula is (C nH 2nO) bPolyoxy alkylidene, wherein n is 2-4, comprises end value,
B is greater than 2, and perhaps the scope of b can be 2-200, and perhaps the scope of b can be 2-100.
Polyoxy alkylidene typically can comprise oxygen ethylidene unit (C 2H 4O), oxygen propylidene unit (C 3H 6O), oxygen butylidene or oxygen tetramethylene unit (C 4H 8Or its mixture O).So R 2-Y 3-R 2The optional self-drifting of compound is R 2-[(C 2H 4O) c(C 3H 6O) d(C 4H 8O) e]-R 2Polyoxy alkylidene, wherein the scope of c, d and e can be 0-200 separately independently, condition be the c+d+e sum greater than 2, perhaps the scope of c+d+e sum is 2-200, perhaps the scope of c+d+e sum is 2-100.
Perhaps, polyoxy alkylidene only comprises oxygen propylidene unit (C 3H 6O) dThe R that contains the polyoxy propylidene 2-Y 3-R 2The representative non-limiting example of compound comprises:
H 2C=CHCH 2[C 3H 6O] dCH 2CH=CH 2
H 2C=CH[C 3H 6O] dCH=CH 2
H 2C=C(CH 3)CH 2[C 3H 6O] dCH 2C(CH 3)=CH 2
HC≡CCH 2[C 3H 6O] dCH 2C≡CH
HC≡CC(CH 3) 2[C 3H 6O] dC(CH 3) 2C≡CH
Wherein d as defined above.
The R that contains polyoxy butylidene or poly-(oxygen tetramethylene) 2-Y 3-R 2The representative non-limiting example of compound comprises:
H 2C=CHCH 2[C 4H 8O] eCH 2CH=CH 2
H 2C=CH[C 4H 8O] eCH=CH 2
H 2C=C(CH 3)CH 2[C 4H 8O] eCH 2C(CH 3)=CH 2
HC≡CCH 2[C 4H 8O] eCH 2C≡CH
HC≡CC(CH 3) 2[C 4H 8O] eC(CH 3) 2C≡CH
B component) also can be the mixture of various polyethers, i.e. B 3The mixture of component.
In another embodiment, component (B) is selected from R 2-Y 4-R 2Compound is expressed as (B herein 4), R wherein 2As defined above, and Y 4It is the polyalkylene that is selected from C2-C6 alkylidene unit or its isomer.An example is poly-isobutylidene, and it is the polymkeric substance that contains the isobutylidene unit.The molecular weight of poly-isobutylidene can change, but scope typically is 100-10,000g/mol.The R that contains poly-isobutylidene 2-Y 4-R 2The representative non-limiting example of compound comprises with trade(brand)name OPPONOL BV available from those of BASF, OPPONOL BV 5K for example, and a kind of molecular-weight average is the polyisobutene of the diallyl end-blocking of 5000g/mol.
In yet another embodiment, component (B) is selected from R 2-Y 5-R 2Compound is expressed as (B herein 5), R wherein 2As defined above, and Y 5It is hydrocarbon-silicone copolymers base.The general formula of hydrocarbon-silicone copolymers base can be:
-[R 1 u(R 2SiO) v] q-
R wherein 1With R as defined above;
U and v independently 〉=1, perhaps the scope of u is 1-20, perhaps the scope of v is 2-500, or 2-200,
Q〉1, perhaps the scope of q is 2-500, perhaps the scope of q is 2-100.
Can be by α, ω-unsaturated hydrocarbons is described as B more than for example 1Those, and the hydrosilylation reactions between the organic radical hydrogen siloxane, preparation has the R of hydrocarbon-silicone copolymers base 2-Y 5-R 2Compound.The representative non-limiting example of this reaction is as follows.
Figure G2007800075754D00101
Component (B) also can be the mixture of any diene, diine or alkene-alkine compounds, for example B 1, B 2, B 3, B 4And B 5Any combination.
The consumption of the preparation employed component of the present composition (A) and component (B) depends on the ratio of independent component and required SiH and aliphatic unsaturated group.The ratio of the SiH in the component (A) that can use of the preparation present composition and the aliphatic unsaturated group of component (B) can be 10:1 to 1:10, perhaps 5:1 is to 1:5, perhaps 4:1 is to 1:4.
If component (A) and (B) be not to contain aliphatic unsaturated group in the composition and unique material of containing the SiH base, then above-mentioned ratio relates to the total amount of this group that exists rather than those components only in composition.
(C) hydrosilylation catalysts
Component (C) comprises any catalyzer that hydrosilylation reactions typically uses.The preferred catalyzer that uses the platinum group metal.Platinum family refers to ruthenium, rhodium, palladium, osmium, iridium and platinum and complex compound thereof.The catalyzer that can be used for preparing the platinum group metal of the present composition is the platinum complex for preparation described in the people's such as the U.S. Patent No. 3419593 of Willing and Brown the U.S. Patent No. 5175325, wherein each piece of writing is introduced by reference at this, so that this complex compound and preparation thereof to be described.Other examples of the catalyzer of useful platinum group metal can be in the people's such as Lee U.S. Patent No. 3989668, the people's such as Chang U.S. Patent No. 5036117, the U.S. Patent No. 3159601 of Ashby, the U.S. Patent No. 3220972 of Lamoreaux, the people's such as Chalk U.S. Patent No. 3296291, the U.S. Patent No. 3516946 of Modic, find in the people's such as the U.S. Patent No. 3814730 of Karstedt and Chandra the U.S. Patent No. 3928629, all these are introduced by reference at this, so that the Catalysts and its preparation method of useful platinum group metal to be described.The catalyzer of platiniferous can be platinum; At carrier, the platinum that for example deposits on silica gel or the powdered carbon; Or the compound of platinum metals or complex compound.Preferred catalyst made from platonic comprises or the Platinic chloride of six hydrated forms or anhydrous form, and or make Platinic chloride and aliphatic unsaturated organosilicon compounds by comprising, the catalyst made from platonic of the method acquisition of divinyl tetramethyl disiloxane reaction for example; Or as the alkene-platinum described in the U.S. Patent application No.10/017229 that submits in December 7 calendar year 2001-silyl complex compound, for example (COD) Pt (SiMeCl 2) 2, wherein COD is that 1,5-cyclooctadiene and Me are methyl.Can be for example by mixing 0.015mol (COD) PtCl 2With 0.045molCOD and 0.0612molHMeSiCl 2, prepare these alkene-platinum-silyl complex compound.
The suitable amounts of catalyzer depends on employed special catalyst.The amount of platinum catalyst should be enough to provide at least hundred 2/10000ths parts (ppm) based on the overall weight percent of solid in the composition (compositions of all non-solvents), preferred 4-200ppm platinum.Highly preferred, based on identical basis, the amount of platinum is enough to provide the 4-150ppm platinum of (weight).Can be used as single species or add catalyzer as the form of mixtures of two or more different plant species.
(D) carrier fluid
Solid elastomers can be included in the optional carrier fluid (D).Although do not require, typically carrier fluid can with carry out the employed solvent phase of above-described hydrosilylation reactions with.Suitable carrier fluid comprises the siloxanes of straight chain and ring-type, organic oil, organic solvent, and these mixture.The specific examples of solvent can find in U.S. Patent No. 6200581, is introduced into by reference for this reason.
Typically, carrier fluid is that the range of viscosities under 25 ℃ is 1-1000mm 2The low viscous siloxanes of/s or volatile methyl siloxane or volatility ethylsiloxane or volatility methylethyl siloxanes, hexamethyl cyclotrisiloxane for example, octamethylcyclotetrasiloxane, decamethylcyclopentaandoxane, ten diformazan basic rings, six siloxanes, octamethyltrisiloxane, decamethyl tetrasiloxane, ten dimethyl, five siloxanes, tetradecamethylhexasiloxane, ten hexamethyl, seven siloxanes, seven methyl-3-{ (trimethyl silyl) oxygen base } trisiloxanes, hexamethyl-3, two { (trimethyl silyl) oxygen base } trisiloxanes of 3-, pentamethyl-{ (trimethyl silyl) oxygen base } cyclotrisiloxane, and polydimethylsiloxane, PES-4, polymethy ethylsiloxane, PSI, polydiphenylsiloxane.
Organic solvent can exemplify but be not limited to aromatic hydrocarbons, aliphatic hydrocrbon, alcohol, aldehyde, ketone, amine, ester, ether, dibasic alcohol, glycol ether, alkylogen and aryl halide.Hydrocarbon comprises Permethyl 99A., isohexadecane, Isopar L (C11-C13), Isopar H (C11-C12), Nexbase 2004.Ether and ester comprise Isodecyl Neopentanoate; the enanthic acid DOPCP; Unister E 275; two capryloyl carbonic ethers; the diethylhexyl carbonic ether; propylene glycol n-butyl ether; ethyl-3-ethoxy-c acid esters; propylene glycol methyl ether acetate; PIVALIC ACID CRUDE (25) tridecyl ester; propylene glycol methyl ether acetate (PGMEA); propylene glycol monomethyl ether (PGME); the PIVALIC ACID CRUDE (25) stearyl; hexanodioic acid diisobutyl ester; Wickenol 116; propylene glycol dicaprylate/dicaprate; and Wickenol 155.Be suitable for comprising fat, oil, lipid acid and Fatty Alcohol(C12-C14 and C12-C18) as independent compound or as the extra organic carrier fluid of the composition of carrier fluid.
The consumption of carrier fluid is so that exist 0-98wt% within containing (A) and composition (B) and (D), perhaps 0.5-90wt%, the perhaps carrier fluid of 5-80wt%, wherein (A), (B) and (D) sum be 100wt%.
E) personal care or health care activeconstituents
Component E) is the activeconstituents that is selected from any personal care or the health care activeconstituents." personal care activeconstituents " as used herein refer to for the treatment of hair or skin with provide make up and/or aesthstic advantage and the typical case adds known in the art in personal care formulations as any compound of additive or the mixture of compound." health care activeconstituents " refer to known in the art be used to medicine or medical advantage are provided any compound or the mixture of compound.Therefore, " health care activeconstituents " comprises the material that is regarded as activeconstituents or active pharmaceutical ingredient, as be included in the Code of Federal Regulations, 200-299 part and 300-499 part, title 21, in the I chapter, by United StatesDepartment of Health ﹠amp; Those that Human Services Food and DrugAdministration commonly uses and defines.
Therefore, activeconstituents can be included in intends providing pharmaceutical active or other direct effects in diagnosis, healing, alleviation, treatment or the preventing disease, perhaps human or the structure of other animal bodies or any component of any function of impact.This wording can be included in and may experience chemical transformation in the preparation of medicine and be present in those components in the medicine with the modified form of intending providing regulation activity or effect.
Some representative example of activeconstituents comprise: medicine, VITAMIN, mineral, hormone, topical anti-microbial agent, for example treat Antibacterial Constituents, the Active antifungal compound of athletic pin, jock itch or tinea and acne activeconstituents; The astringent matter activeconstituents; The deodovization agent activeconstituents; Except wart agent activeconstituents; Corn and callus remover activeconstituents; The pediculicide activeconstituents for the treatment of head louse, crab louse and body louse; Control head scurf, seborrheic dermatitis or psoriasic activeconstituents; With sunburn prevention and therapeutical agent.
The useful activeconstituents that uses in the method for the invention comprises VITAMIN and derivative thereof, comprising " pro-vitamin ".Useful herein VITAMIN includes, but are not limited to vitamin A 1, Vogan-Neu, Vogan-Neu C2-C18 ester, vitamin-E, tocopherol, vitamin-E ester, and composition thereof.Vogan-Neu comprises trans-Vogan-Neu, 1,3-cis-Vogan-Neu, 11-cis-Vogan-Neu, 9-cis-Vogan-Neu and 3,4-, two dehydrogenations-Vogan-Neu, vitamins C and derivative thereof, vitamins B 1, vitamins B 2, dexpanthenol, panthenol, vitamins B 6, vitamins B 12, nicotinic acid, folic acid, vitamin H and pantothenic acid.The VITAMIN that other that herein comprise are suitable and the INCI title of the VITAMIN that is considered are two ascorbyl palmitates, methyl-monosilane alcohol pectic acid acid ascorbyl ester, ascorbyl palmitate, ascorbyl stearate, ascorbigen glucoside, SAP, sodium ascorbate, sulfuric acid acid ascorbyl ester disodium, (xitix/tocopherol) phosphoric acid ester potassium.
Should be noted that Vogan-Neu is by The Cosmetic, Toiletry, andFragrance Association (CTFA), Washington DC is for the world name (INCI) of the cosmetic composition title of vitamin A appointment.The VITAMIN that other that herein comprise are suitable and the title of the VITAMIN that is considered are retinoic acid ester, retinyl palmitate, Vitamin A propionate, alpha-tocopherol, TOCOPHERSOLAN, acetic acid tocoretinate, linolic acid tocoretinate, nicotinic acid tocoretinate and succsinic acid tocoretinate.
Some examples that are suitable for commercially available product used herein are retinyl acetate and vitamins C, and the two all is Sweden Fluka Chemie AG, the product of Buchs; COVI-OX T-50, a kind of Henkel Corporation, La Grange, the vitamin-E product of Illinois; COVI-OXT-70, Henkel Corporation, La Grange, the another kind of vitamin-E product of Illinois; And vitamin e acetate, a kind of RocheVitmins ﹠amp; Fine Chemicals, Nutley, the product of New Jersey.
The activeconstituents that uses in the method for the invention can be active pharmaceutical ingredient.The representative example of more spendable suitable active pharmaceutical ingredients is hydrocortisones, Ketoprofen, timolol, pilocarpine, Zorubicin, ametycin, morphine, hydromorphone, Odizem, theophylline, Doxorubicin, daunorubicin, heparin, penicillin G, Gepcillin, cefoxitin, the cephalo tincture, cefotaxime, 5 FU 5 fluorouracil, cytosine arabinoside, the 6-azauridine, 6-thioguanine, vinealeucoblastine(VLB), vincristine(VCR), bleomycin sulfate, gold thioglucose, Suramine, mebendazole, clonidine, Scopolamine, Proprasylyte, Phenylpropanolamine, hydrochloride, Strophanthin G, haloperidol, Isosorbide, pannonit, Ibuprofen BP/EP, ubiquinone, indomethacin, prostanoid, Naproxen Base, salbutamol, guanabenz, Trate, pheniramine, Trichlorphon and steroid.
For purpose of the present invention, comprise herein what be considered as active pharmaceutical ingredient is anti-acne agents, for example benzoyl peroxide and tretinoin; Antibacterial agent, for example chlorine hexadiene gluconate; Anti-mycotic agent, for example miconazole nitrate; Antiphlogistic; The corticosteroid medicine; Non-steroid antiphlogistic, for example Diclofenac Sodium; Psoriasis medicine, for example Temovate; Narcotic, for example lignocaine; Antipruritic; Anti-dermatitis agent; Usually be considered as the reagent of barrier film.
Active ingredient E of the present invention) can be protein, for example enzyme.Comprise that in silicone elastomer gels the advantage that enzyme has is, prevent enzyme deactivation and keep for a long time the biological activity effect of enzyme.The variant that enzyme includes, but not limited to commercially available type, improves type, recombinant type, agriotype, occurring in nature can not find, and composition thereof.For example, suitable enzyme comprises lytic enzyme, at, oxydase, transferring enzyme, reductase enzyme, hemicellulase, esterase, isomerase, polygalacturonase, Sumylact L, peroxidase, laccase, catalase and composition thereof.Lytic enzyme includes but not limited to proteolytic enzyme (bacterium, fungi, acid, neutrality or alkalescence), amylase (α or β), lipase, seminase, cellulase, collagenase, N,O-Diacetylmuramidase, superoxide-dismutase, catalase and composition thereof.Described proteolytic enzyme includes but not limited to trypsinase, Quimotrase, stomach en-, pancreatin and other mammalian enzyme; Papoid, bromeline and other plant enzyme; Subtilisin, epidermin, nisin, naringinase (L-rhammnosidase) urokinase and other bacterial enzyme.Described lipase includes but not limited to triacylglycerol lipase, monoacylglycerol lipase, lipoprotein lipase, for example steapsin, erepsin, stomach en-, other Mammals, plant, comprising lipase of bacterial origin and purifying substance.Preferred natural papoid is as described enzyme.In addition, stimulate hormone, for example Regular Insulin can use with these enzymes, increases their validity.
Component E) also can be sun-screening agent.Sun-screening agent can be selected from protection skin known in the art in order to avoid be exposed to any sun-screening agent of the harmful effect under the sunlight.Sun screening compound typically is selected from organic compound, mineral compound or its mixture of absorbing ultraviolet light (UV).Therefore; the representative non-limiting example that can be used as sun-screening agent comprises benzaminic acid, to methoxy styracin-2-ethoxy ethyl ester, diethanolamine Methoxycinnamate, two galloyl trioleates, dioxybenzone, 4-[two (hydroxypropyl)] subcutin, glyceryl aminobenzoate, Uniderm Homsal, the 2 hydroxy 1,4 naphthoquinone (lawsone) that contains otan, anthranilic acid
Figure G2007800075754D0015114649QIETU
Ester; Octocrilene; octyl methoxycinnamate; octyl salicylate; oxybenzone; dimethyl amido amyl benzoate 0; the sulphenyl benzoglyoxaline; red petrolatum; sulisobenzone; titanium dioxide and triethanolamine salicylate; cetaminosalol; the wallantoin para-amino benzoic acid; the benzal phthalide; benzophenone; benzophenone 1-12; 3-benzal camphor; benzal camphor hydrolytic collagen sulphonamide; the benzal camphorsulfonic acid; benzyl salicylate; bornelone; bumetrizole (Bumetriozole); PAROSOL 1789; planoform; cerium oxide/silicon-dioxide; cerium oxide/silicon-dioxide/talcum; to methoxy styracin-2-ethoxy ethyl ester; the DEA-Methoxycinnamate; two benzoxazoles naphthalenes; di-t-butyl hydroxyl benzal camphor; two galloyl trioleates; the tolyl acrylic acid diisopropyl ester; dimethyl para-amino benzoic acid ethyl cetostearyl dimethylammonium tosylate; UVASORB HEB; phenylbenzene methoxy base acetoxyl group aphthopyrans; two ethylphenyl triamino triazine stilbene disulfonic acid disodiums; diphenylethyllene phenylbenzene triamino triazine stilbene disulfonic acid disodium; diphenylethyllene phenylbenzene disulfonic acid disodium; drometrizole; the drometrizole trisiloxanes; para-amino benzoic acid ethyl dihydroxypropyl ester; the di-isopropyl ethyl cinnamate; the methoxy cinnamic acid ethyl ester; parathesin; the urocanic acid ethyl ester; 2-cyano group-3, the 3-diphenylacrylate is ester; forulic acid; the glyceryl octanoate; the dimethoxy-cinnamic acid ester; para-amino benzoic acid glyceryl ester; glyceryl salicylate; Uniderm Homsal; Neo Heliopan E1000; Whitfield's ointment sec.-propyl benzyl ester; isopropyl diphenyl formyl radical methane; the methoxy cinnamic acid isopropyl ester; anthranilic acid
Figure G2007800075754D00161
Ester, Whitfield's ointment Ester, 4-methyl benzal, camphor, Viosorb 930, Octrizole, para-amino benzoic acid octyldimethyl ester, octyl methoxycinnamate, octyl salicylate, UVINUL T-150, para-amino benzoic acid, PEG-25 para-amino benzoic acid ester, para-amino benzoic acid amyl group dimethyl ester, Phenylbenzimidazolesulfonic acid, polyacrylamide ylmethyl benzal camphor, methoxy cinnamic acid potassium, Phenylbenzimidazolesulfonic acid potassium, red petrolatum, Phenylbenzimidazolesulfonic acid sodium, urocanic acid sodium, TEA-Phenylbenzimidazolesulfonic acid salt, the TEA-salicylate, the Terephthalidene Dicamphor Sulfonic Acid, titanium dioxide, zinc oxide, cerium dioxide, three para-amino benzoic acid panthenols, urocanic acid and VA/ crotonate/methacryloxy BP-1 multipolymer.
Sun-screening agent can be single a kind of or greater than a kind of combination.Perhaps, sun-screening agent is styracin ester group organic compound, and perhaps sun-screening agent is OMC, for example
Figure G2007800075754D00163
MC80, the ester of a kind of p-methoxycinnamic acid and 2-Ethylhexyl Alcohol.
Component E) also can be spices or essence.Spices can be any spices or essence activeconstituents commonly used in perfume industry.These components typically belong to various chemical types, for example with alcohol, aldehyde, ketone, ester, ether, acetic ester, nitrous acid ester, terpene hydrocarbon, heterocycle is nitrogenous or sulphur compound, and the essential oil variation in natural or synthetic source.At the standard textbook reference, Perfume and Flavour Chemicals for example, 1969, S.Arctander, Montclair has described many in these perfume ingredients in detail among the New Jersey.
Spices can exemplify but be not limited to aromatic ketone and aromatic aldehyde.The example of aromatic ketone is buccoxime, isojasmone, methyl-betanaphthyl ketone, muskone, tonalide, α-damascone, β-damascone, δ-damascone, different-damascone, damascenone, large horse rose ketone (Damarose), methyl-Dihydrojasmone acid esters, piperitone, Karvon, camphor, fenchone, α-ionone, alpha, beta-lonone, the so-called jononeionone of γ-methyl, fleuramone, Dihydrojasmone, LINL-OX, ambrotone, methyl-cypress thiazolinyl-ketone or methyl-cedrone, methyl phenyl ketone, methyl-acetophenone, p-methoxyl group-methyl phenyl ketone, methyl-betanaphthyl-ketone, benzyl-acetone, benzophenone, p-hydroxyl-phenyl-butanone, apione, 6-sec.-propyl decahydro-2-naphthalenone, dimethyl-octene ketone, bright piperitone (Freskomenthe), 4-(1-vinyl ethyl ether base)-3,3,5,5 ,-tetramethyl--pimelinketone, methyl-heptenone, 2-(2-(4-methyl-3-tetrahydrobenzene-1-yl) propyl group)-cyclopentanone, 1-is (right
Figure G2007800075754D00171
Alkene-6 (2)-yl)-1-acetone; 4-(4-hydroxy 3-methoxybenzene base)-2-butanone; 2-ethanoyl-3; 3-dimethyl-norbornane; 6; 7-dihydro-1; 1; 2; 3; 3-pentamethyl--4 (5H)-2; the 3-bihydrogen-1-indenone; 4-damascol; piperonylacetone; 2-hexyl methyl aceto acetate (Gelsone); allyl ionone (Hexalon); ambrotone; methyl cyclocitrone; methyl-lavender-ketone; 4-tert-pentyl pimelinketone (Orivon); p-tertiary butyl pimelinketone; 2-tertiary butyl pimelinketone (Verdone); 2-amyl group cyclopentanone (Delphone); muskone; new methylene acetone; medicine ketone musk (Plicatone); all roads ketone (Veloutone); 2; 4; 4; 7-tetramethyl--oct-6-ene-3-ketone and 3; 4; 5,6-tetrahydropseudoionone (Tetrameran).
More preferably aromatic ketone is selected from α-damascone, δ-damascone, different damascone, Karvon, γ-methyl-jononeionone, ambrotone, 2 according to its odor characteristics, 4,4,7-tetramethyl--oct-6-ene-3-ketone, benzyl acetone, β-damascone, damascenone, methyl dihydrojasmonate, vertofix coeur and composition thereof.
Preferably, aromatic aldehyde is selected from 2 according to its odor characteristics, 6,10-trimethylammonium hendecene-9-aldehyde-1, aubepine, cymal, vanillal, cyanine aldehyde, helional, piperonylaldehyde, laurine, ethanoyl two polyisoamylenes (koavone), lauryl aldehyde, LYRAL (lyral), methyl nonyl acetaldehyde, fragrance acetaldehyde (P.T.bucinal), phenyl acetaldehyde, undecylene aldehyde, Vanillin, 2,6,10-trimethylammonium-9-undecylene aldehyde, 3-laurylene-1-aldehyde, α-n-pentyl phenylacrolein, 4-methoxybenzyl aldehyde, benzyl aldehyde, 3-(4-tert-butyl-phenyl)-propionic aldehyde, 2-methyl-3-(p-p-methoxy-phenyl propionic aldehyde, 2-methyl-4-(2,6,6-trimethylammonium-2 (1)-tetrahydrobenzene-1-yl) butyraldehyde, 3-phenyl-2-propenal, suitable/anti--3,7-dimethyl-2,6-octadiene-1-aldehyde, 3,7-dimethyl-6-octene-1-aldehyde, [(3,7-dimethyl-6-octenyl) oxygen base] acetaldehyde, 4-sec.-propyl benzyl aldehyde, 1,2,3,4,5,6,7,8-octahydro-8,8-dimethyl-2-naphthaldehyde, 2,4-dimethyl-3-tetrahydrobenzene-1-aldehyde, 2-methyl-3-(isopropyl phenyl) propionic aldehyde, the 1-capraldehyde; Capraldehyde, 2,6-dimethyl-5-heptenal, ([5.2.1.0 (2 for three rings for 4-, 6)]-Ya decyl-8)-butyraldehyde, octahydro-4,7-methylene radical-1H-indenes aldehyde, 3-oxyethyl group-4-hydroxyl benzyl aldehyde, p-ethyl-α, the alpha-alpha-dimethyl hydrocinnamic aldehyde, Alpha-Methyl-3,4-(methylene radical dioxy base)-hydrocinnamic aldehyde, 3,4-methylene radical dioxy base benzyl aldehyde, α-n-hexyl phenylacrolein, between loose flower hydrocarbon (meta-loose colored hydrocarbon)-7-aldehyde, Alpha-Methyl phenyl acetaldehyde, 7-hydroxyl-3,7-dimethyl octanal, undecylene aldehyde, 2,4,6-trimethylammonium-3-tetrahydrobenzene-1-aldehyde, 4-(3) (4-methyl-3-pentenyl)-3-tetrahydrobenzene-aldehyde, the 1-lauric aldehyde, 2,4-dimethyl tetrahydrobenzene-3-aldehyde, 4-(4-hydroxy-4-methyl amyl group)-3-tetrahydrobenzene-1-aldehyde, 7-methoxyl group-3,7-dimethyl-octa-1-aldehyde, the 2-methyl undecyl aldehyde, Aldehyde C-11 MOA, the 1-aldehyde C-9, the 1-octanal, 2,6,10-trimethylammonium-5, the 9-undecadienal, 2-methyl-3-(the 4-tertiary butyl) propionic aldehyde, dihydro cinnamon aldehyde, 1-methyl-4-(4-methyl-3-pentenyl)-3-tetrahydrobenzene-1-aldehyde, 5 or 6 methoxyl group 10-six hydrogen-4,7-methylene radical indane-1 or 2-aldehyde, 3,7-dimethyl-octa-1-aldehyde, the 1-undecyl aldehyde, 10-hendecene-1-aldehyde, 4-hydroxy-3-methoxy benzyl aldehyde, 1-methyl-3-(4-methyl amyl)-3-hexamethylene olefine aldehydr, 7-hydroxyl-3,7-dimethyl-octanal, trans-the 4-decenal, 2,6-nonadienal, p-methylphenyl acetaldehyde; 4-aminomethyl phenyl acetaldehyde, 2-methyl-4-(2,6,6-trimethylammonium-1-tetrahydrobenzene-1-yl)-crotonic aldehyde, ortho-, meta-or p-methoxycinnamic aldehyde, 3,5,6-trimethylammonium-3-hexamethylene olefine aldehydr, 3,7-dimethyl-2-methylene radical-6-octenal, phenoxy acetaldehyde, 5,9-dimethyl-4, the 8-decadienal, tree peony aldehyde (6,10-dimethyl-3-oxygen-5,9-11 carbon diene-1-aldehyde), six hydrogen-4,7-methylene radical indane-1-aldehyde, 2-methyl aldehyde C-9, Alpha-Methyl-4-(1-methylethyl) phenylacetic aldehyde, 6, firpene-2-propionic aldehyde falls in 6-dimethyl-2-, to the methylenedioxy phenoxy ethylhexanal, 2-methyl-3-phenyl-2-propylene-1-aldehyde, 3,5,5-trimethylammonium hexanal, six hydrogen-8,8-dimethyl-2-naphthaldehyde, 3-propyl group-dicyclo [2.2.1]-heptan-5-alkene-2-aldehyde, the 9-decenal, 3-methyl-5-phenyl-1-valeral, methyl nonyl acetaldehyde, hexanal, trans-the 2-hexenoic aldehyde, 1-p-
Figure G2007800075754D00181
Alkene-q-aldehyde and composition thereof.
Preferred aldehyde is selected from 1-capraldehyde, benzyl aldehyde, cyanine aldehyde, 2 according to its odor characteristics, 4-dimethyl-3-tetrahydrobenzene-1-aldehyde; Suitable/anti--3,7-dimethyl-2,6-octadiene-1-aldehyde, piperonylaldehyde; 2,4,6-trimethylammonium-3-tetrahydrobenzene-1-aldehyde; 2,6-nonadienal, α-n-pentyl phenylacrolein, α-n-hexyl phenylacrolein, fragrant acetaldehyde, LYRAL, cymal, methyl nonyl acetaldehyde, hexanal, trans-2-hexenoic aldehyde and composition thereof.
In perfume composition listed above, some are the conventional known trade(brand)names of those skilled in the art, and also comprise isomer.This isomer also is suitable for using in the present invention.
Component E) also can be one or more Plant Extracts.The example of these components is as described below: the angelica keiskei koidzumi extract, the avocado extract, the Flower of Largeleaf Hydrangea extract, the Root of Hollyhock extract, the arnica extract, Aloe extract, Fructus Pruni extract, the almond extract, Semen Ginkgo extract, Fructus Foeniculi extract, Rhizoma Curcumae Longae extract, oolong tea extract, seek real extract, the Echinacea purpurea Moench extract, the scutellariae,radix extract, the Berberis Amurensis Rupr extract, the coptis japonica Makino extract, Fructus Hordei Vulgaris extract, Fructus Forsythiae extract, white nettle extract, the Nasturtium officinale extract, citrus extracts, the salt water of dehydration, Seaweed Extract, elastin hydrolysis, the hydrolyzed wheat powder, hydrolysis silk, Flos Chrysanthemi extract, Radix Dauci Sativae extract, the artemisia extract, Radix Glycyrrhizae extract, rose of Sharon extract, fire sour jujube berry extract, Fructus actinidiae chinensis extract, the Peruvian bark extract, Fructus Cucumidis sativi extract, guanosine, Fructus Gardeniae extract, Folium Bambosae extract, the Sophora root extract, Walnut extract, grapefruit abstract, the Root of Cream Clematis extract, chlorella extract, mulberry extract, Radix Gentianae extract, black tea extract, yeast extract, burdock extract, rice bran ferment extract, rice embryo oil, the comfrey extract, collagen, Pericarpium Citri tangerinae extract, Fructus Gardeniae extract, the Radix Asari extract, Bupleurum class extract, the umbilical cord extract, sage extract, the Saponaria officinalis extract, bamboo extractive, the hawthorn fruit extract, the Chinese prickly ash fruit extract, assorted Plutarch mushroom extract, the Radix Rehmanniae extract, Radix Arnebiae extract, Folium perillae extract, the linden extract, the palmate meadowsweet extract, peony extract, the Rhizoma Acori Graminei extract, the white birch extract, the horse hair extract, ivy helix (Ivy) extract, Fructus Crataegi extract, the golden elder extract, the milfoil extract, the Mentha arvensis L. syn.M.haplocalyxBrig extract, the Arisaema balansae Engl. grass extract, the high mallow extract, the Ligusticum wallichii root extract, the green Radix Gentianae extract of Japan, soybean extraction, the jujube extract, Thymi Serpylli Herba extract, tea extract, Flos Caryophylli extract, Gramineae cogongrass extract, both citrus satsuma orange peel extract, Angelica roots, the Mary-bud extract, Semen Persicae extract, the bitter orange peer extract, Herba Houttuyniae extract, the tomato extract, natto extract, Radix Ginseng extract, tea extract, curried extract, the rose extract, the lotus extract, the tuber of dwarf lilyturf tuber extract, the lotus extract, parsley extract, honey, the witch hazel extract, the Parietaria extract, Herba Rabdosiae Lophanthoidis extract, the bisabolol extract, the loquat extract, the coltsfoot extract, the Petasites Gaertner extract, Poria extract, the Flower of Chinese Peashrub extract, propolis extract, Fructus Luffae extract, Flos Carthami extract, Folium Menthae extract, the lime tree extract, the Paeonia extract, Flos lupuli (Flos Humuli Lupuli) extract, pine extract, the horse-chestnut extract, may examine and add weasel taro (Lysichiton camtschatcese) extract, the Seed of Chinese Soapberry peel extract, the Herba melissae axillaris extract, the peach extract, the Minor centaury extract, eucalyptus extracts, Herba Saxifragae extract, the citron extract, the Coix extract, the mugwort extract, the lavender extract, Fructus Mali pumilae extract, Caulis et Folium Lactucae sativae extract, citron extract, the Herba Astragali Melilotoidis (Herba Astragali Sinici) extract, rose extract, rosemary extract, Rome chamomile extract and royal jelly extract.
The component E that exists in silicone gel composition) consumption can change, but typically as described below:
Based on the weight of the silicone elastomer gels that exists in the composition, that is the component A in silicone gel composition), B), C) and gross weight D), be 0.05-50wt%, perhaps 1-25wt%, perhaps 1-10wt%.
Activeconstituents, component E) can or in the preparation process of silicone elastomer (preload method) add in the silicone gel composition, perhaps (back loading method) adds in the silicone gel composition after forming silicone elastomer gels.
The preload method relates to:
I) make the following substances reaction:
A) have the organic radical hydrogen cyclosiloxane of at least two SiH unit at the siloxanes ring,
B) in its molecule, have the compound of at least two aliphatic unsaturated hydrocarbon bases,
C) hydrosilylation catalysts
Form:
A) in its molecule, have the organic radical hydrogen siloxane of the cyclosiloxane ring that contains at least two SiH,
Wherein component a) in SiH unit and B component) in the molar ratio range of aliphatic unsaturated hydrocarbon base be 2/1-8/1,
II) at D) optional carrier fluid and E) make in the presence of personal care or the health care activeconstituents:
A) in its molecule, have the organic radical hydrogen siloxane of the cyclosiloxane ring that contains at least two SiH, with extra consumption
B) in its molecule, have the compound of at least two aliphatic unsaturated hydrocarbon bases or the mixture of compound,
C) hydrosilylation catalysts
Reaction forms silicone elastomer gels.
The back loading method relates to:
I) make the following substances reaction:
A) have the organic radical hydrogen cyclosiloxane of at least two SiH unit at the siloxanes ring,
B) in its molecule, have the compound of at least two aliphatic unsaturated groups or the mixture of compound,
C) hydrosilylation catalysts
Form:
A) in its molecule, have the organic radical hydrogen siloxane of the cyclosiloxane ring that contains at least two SiH,
Wherein component a) in SiH unit and B component) in the molar ratio range of aliphatic unsaturated group be 2/1-8/1,
II) at D) in the presence of the optional carrier fluid, further make:
A) in its molecule, have the organic radical hydrogen siloxane of the cyclosiloxane ring that contains at least two SiH, with extra consumption
B) in its molecule, have the compound of at least two aliphatic unsaturated groups,
C) hydrosilylation catalysts
Reaction forms silicone elastomer gels,
III) mix
E) personal care or health care activeconstituents and this silicone elastomer gels form the silicone elastomer gels that contains activeconstituents.
Silicone elastomer
Silicone elastomer of the present invention can be with component A), B) and hydrosilylation reactions product form C) obtain.Term " hydrosilylation " refers at catalyzer (for example component C)) in the presence of, addition contains the organic radical silicon compound (for example, component A) with the hydrogen of silicon bonding) to the compound that contains aliphatic unsaturated link(age) (for example B component).Hydrosilylation reactions is known in the art, and any this known method or technology can be used for carrying out component A), B) and hydrosilylation reactions C), prepare silicone elastomer of the present invention.
Can in the presence of solvent, carry out hydrosilylation reactions, and subsequently by known technology desolventizing.Perhaps, can in solvent, carry out hydrosilylation, wherein solvent with as optional component D) described carrier fluid is identical.
Perhaps, can prepare silicone elastomer by the method that comprises the steps:
I) make the following substances reaction:
A) have the organic radical hydrogen cyclosiloxane of at least two SiH unit at the siloxanes ring,
B) in its molecule, have the compound of at least two aliphatic unsaturated hydrocarbon bases or the mixture of compound,
C) hydrosilylation catalysts
Form:
A) in its molecule, have the organic radical hydrogen siloxane of the cyclosiloxane ring that contains at least two SiH,
Wherein component a) in SiH unit and B component) in the molar ratio range of aliphatic unsaturated group be 2/1-8/1, perhaps be 2/1-6/1, perhaps be 3/1-4/1;
II) further make:
A) in its molecule, have the organic radical hydrogen siloxane of the cyclosiloxane ring that contains at least two SiH, with extra consumption
B) in its molecule, have the compound of at least two aliphatic unsaturated hydrocarbon bases or the mixture of compound,
C) hydrosilylation catalysts
Reaction forms silicone elastomer gels.
Component A), B), C) with above-described identical.In addition, can with the above similar condition under react.At abovementioned steps II) in, component A) in SiH unit and B component) in the molar ratio range of aliphatic unsaturated group be 10/1-1/10, perhaps 5/1-1/5, perhaps 4/1-1/4.
The composition that contains the gelling of organic silicone elastomer
Silicone elastomer can be joined that carrier fluid (above as component D) describes) in, form the composition of gelling, perhaps at first can in independent reaction, prepare silicone elastomer, then it is joined in the carrier fluid, obtain gel.The feature of the composition of gelling of the present invention can be its hardness or solidness.The useful test that characterizes gel is those of GelatinManufacturers Institute of America recommendation, for example uses " TextureAnalyzer " (model TA.XT2, Stable Micro Systems, Inc., Godalming, Britain).The Texture Analyzer that employing has with the probe of 5.0kg load cell carries out compression testing to gel sample.Probe near gel surface, and continues to be compressed to the distance of 5.0mm in the gel with the speed of 0.5mm/sec, then keeps for 1 second before processing again.Texture Analyzer detects the resistance that stands at compression testing process middle probe.As the function of time, to the masterpiece figure that shows by load cell.
For purpose of the present invention, the hardness of silicone elastomer, gel and elastomer blend (SEB) is defined as the resistance that passes through the probe in detecting in " Texture Analyzer " in the compression testing process.Can use two data to characterize hardness: power 1, the power during maximum compression point (entering the point of compression of 5.0mm in the gel surface), and area F-T: the integration of area-Li in 1 second process of maximum compression point place maintenance.Typically for each gel, amount to the average of 5 tests.
By firmly value (g) is divided by 101.97 (namely 1 newton equals 101.97g power, based on the size of employed probe in this instrument), the data reduction that power 1 is obtained becomes newton (N).It is area F-T1:2 that Texture Analyzer measures the second performance report, the g of unit power second.This is that power is to the area integral of test period curve.This performance is the indication of gel network, because it shows the ability that keeps compression resistance force, this is relevant with elastomerics and gel.Report this numerical value take g power second as unit, and by divided by 101.97, changing into ox second (SI units) with this numerical value (g of unit power second).
The compressive hardness of silicon gel of the present invention is 200N/m at least 2, perhaps 400N/m 2, perhaps 600N/m 2
The gel paste composition that contains organic silicone elastomer
The composition of gelling of the present invention can be used for preparing gel paste or the gel blend composition that contains activeconstituents, and it passes through:
I) shear aforesaid silicone elastomer gels,
II) in conjunction with the silicone elastomer gels of this shearing and extra consumption
D) aforesaid carrier fluid, and randomly
E) individual or health care activeconstituents,
Form gel paste or blend composition.
Silicone elastomer gels composition of the present invention can be considered the discrete crosslinked silicone elastomer gels particle that disperses in carrier fluid.Therefore, elastomer silicone composition is the effective rheology thickening material that the organosilicon fluid of lower molecular weight is used.Just because of this, can use them to be prepared with the gel blend composition of usefulness, for example " paste " composition.
In order to prepare this silicone elastomer blend, shear the aforementioned silicone elastomer gels with known initial elastomer content (IEC), obtain little granularity and further be diluted to final elastomer content (FEC)." shearing " as used herein refers to any shear-mixed method, for example available from homogenizing, supersound process or any other blending means as shear-mixed known in the art.The shear-mixed of silicone elastomer gels composition causes having the composition that reduces granularity.Have subsequently reduce granularity composition further with D) carrier fluid merges.Carrier fluid can be above-described any carrier fluid, but typically is volatile methyl siloxane, for example D5.Being used in conjunction with D) carrier fluid is not crucial with the technology with the elastomer silicone composition that reduces granularity, and typically relates to simple agitation or mixing.Resulting composition can be regarded as paste, and its viscosity is greater than 100,000cP (mPas).
Embodiment
For the person of ordinary skill of the art, these embodiment intend setting forth the present invention, and should not be interpreted as limiting the scope of the present invention of listing in the claim.
The explanation of material
Use in these embodiments following material.
The organic radical hydrogen siloxane
MeH CYCLICS=general formula is [(CH 3) HSiO] xMethylhydracyclosiloxane (MeH ring bodies), wherein the mean value of x is 4.4.
MeH LINEAR=general formula is MD 94D ` 6The organic radical hydrogen polysiloxanes of M
The siloxane polymer that contains unsaturated group
VINYL SILOXANE#1=general formula (CH 2=CH) (CH 3) 2SiO[(CH 3) 2SiO] DpSi (CH 3) 2(CH=CH 2) dimethyl polysiloxane of dimethylvinylsiloxy end-blocking that is, wherein mean polymerisation degree (dp) be 8 and the viscosity under 25 ℃ be 4mm 2/ s.
VINYL SILOXANE #2=general formula is (CH 2=CH) (CH 3) 2SiO[(CH 3) 2SiO] DpSi (CH 3) 2(CH=CH 2) the dimethyl polysiloxane of dimethylvinylsiloxy end-blocking, wherein mean polymerisation degree (dp) be 130 and the viscosity under 25 ℃ be 325mm 2/ s.
VINYL SILOXANE #3=[(CH 2=CH)(CH 3) 2SiO[(CH 3) 2SiO] 30] 4Si
VINYL SILOXANE #4=tetramethyl-tetrem thiazolinyl cyclotetrasiloxane [(CH 2=CH) (CH 3) SiO] 4
VINYL SILOXANE #5=general formula is (CH 2=CH) (CH 3) 2SiO[(CH 3) 2SiO] DpSi (CH 3) 2(CH=CH 2) the dimethyl polysiloxane of dimethylvinylsiloxy end-blocking, wherein mean polymerisation degree (dp) be 27 and the viscosity under 25 ℃ be 25mm 2/ s.
VINYL SILOXANE #6=general formula is (CH 2=CH (CH 2) 4) (CH 3) 2SiO[(CH 3) 2SiO] DpSi (CH 3) 2((CH 2) 4(CH 2=CH)) the dimethyl polysiloxane of dimethyl hexenyl siloxy-end-blocking, wherein mean polymerisation degree (dp) be 37 and the viscosity under 25 ℃ be 40mm 2/ s.
VINYL SILOXANE #7=general formula is (CH 2=CH (CH 2) 4) (CH 3) 2SiO[(CH 3) 2SiO] DpSi (CH 3) 2((CH 2) 4(CH 2=CH)) the dimethyl polysiloxane of dimethyl hexenyl siloxy-end-blocking, wherein mean polymerisation degree (dp) be 100 and the viscosity under 25 ℃ be 170mm 2/ s.
VINYL SILOXANE #8=general formula is (CH 2=CH (CH 2) 4) (CH 3) 2SiO[(CH 3) 2SiO] DpSi (CH 3) 2((CH 2) 4(CH 2=CH)) the dimethyl polysiloxane of dimethyl hexenyl siloxy-end-blocking, wherein mean polymerisation degree (dp) be 200 and the viscosity under 25 ℃ be 730mm 2/ s.
VINYL SILOXANE #9=general formula is (CH 2=CH) (CH 3) 2SiO[(CH 3) 2SiO] DpSi (CH 3) 2(CH=CH 2) the dimethyl polysiloxane of dimethylvinylsiloxy end-blocking, wherein mean polymerisation degree (dp) is 27.
VINYL SILOXANE #10=general formula is (CH 2=CH) (CH 3) 2SiO[(CH 3) 2SiO] DpSi (CH 3) 2(CH=CH 2) the dimethyl polysiloxane of dimethylvinylsiloxy end-blocking, wherein mean polymerisation degree (dp) is 430.
Hydrosilylation catalysts
The Pt catalyzer that uses with the form that provided of 0.52wt%Pt. is provided PT CATALYST=SLY-OFF 4000 (Dow Corning Corporation, Midland MI).
Carrier fluid
Decamethylcyclopentaandoxane or D ring bodies that D5=uses with the form that is provided, DC245 (Dow Corning Corporation, Midland MI).
IDNP=is with the Isodecyl Neopentanoate of trade(brand)name CERAPHYL SLK available from ISP (InternationalSpecialty Products Co).
The IDD=Permethyl 99A.
Stablizer=Vitamin A Palmitate 1.7 M.I.U/Gram (VAP) and Yoshinox BHT (BHT)
Measure the method for the viscosity of silicone elastomer blend (SEB)
For feature class be similar to paste, putty, frost, gelatin or wax material, when using with the suitable Brookfield viscometer of being furnished with special T-rod type spindle, Brookfield Helipath TMIt is the viscosity/consistency measurement of unit that Stand will allow centipoise.
Use has the Brookfield Model RVD-II+ viscometer of Helipath stand (Brookfield Model D) and T-rod spindle (Brookfield Helipath Spindle Set), measures the viscosity of silicone elastomer blend.All these buy the Laboratories in Brookfield Engineering, Inc. (11CommerceBoulevard Middleboro, Massachusetts, USA).
The sample size of requirement 100g in 4 ounces of cylindrical cans.Used following preparation section before measuring: at first by centrifugal, make the sample deaeration, then the vacuum deaeration is 2 hours.After deaeration, 25 ℃ of lower sample minimum 4 hours of regulating.In the center, with T-rod spindle location sample.According to the typical process of Helipath spindle, reading of data.
Usually, for the sample of thickness more not, use spindle 93 (T-rod spindle C), for the sample of thickness relatively, use spindle 95 (T-rod spindle E).Typical set value is 2.5rpm.Spindle speed maintains under the constant 2.5rpm, and changes spindle, the sample that has remarkable viscosity with processing.
The measurement of silicone elastomer gels hardness
Use Texture analyzer (model TA.XT2, Stable Micro Systems, Inc., Godalming,, Britain) and, the hardness (or solidness) of sign silicone elastomer gels.Gelatin Manufacturers Institute of America recommends this test method as standard procedure.
For silicon gel and elastomer blend, the diameter of being made by DELRIN Derlin (Dupont) is that the cylindrical needle of 1/2 inch (1.27cm) is used for measuring.Use probe and following testing campaign, gel sample is carried out compression testing: probe, then kept 1 second before processing near gel surface and continue to be compressed to the distance of 5.0mm in the gel with the speed of 0.5mm/s again.Texture analyzer has the load cell of 5.0kg, detects the resistance that stands at compression testing process middle probe.As the function of time, to the masterpiece figure that demonstrates by load cell.
The hardness of silicone elastomer, gel and elastomer blend (SEB) be defined as in the compression testing process by probe in detecting to resistance.About hardness value, use two data: power 1, the power during maximum compression point (point of compression of 5.0mm in gel surface), and area F-T: the integration of area-Li in 1 second process of maximum compression point place maintenance.Typically for each gel, amount to 5 tests, and report the mean value of 5 tests.
It is power (g of unit) that gel hardness is measured employed Texture analyzer, and this detects by transmodulator.About gel hardness, report two data: power 1, the power (g) of its pre-programmed fully depression in probe arrives gel sample when compression (or) record.The unit of power 1 reading is g power.
Divided by 101.97 (namely 1 newton equals 101.97g power, based on the size of employed probe in this instrument), will be converted into regard to the numerical value of power 1 gained newton (N) by the value (g) of exerting oneself.For example, the numerical value of 6327g power is converted into 62.0N.
The second performance that Texture analyzer reports is area F-T1:2, the g of unit power second.This is that power is to the area integral of test period curve.This is the Performance figure of gel network, because it shows the ability that keeps compression resistance force, this is relevant with elastomerics and gel.
Report this numerical value take g power second as unit, and by with this numerical value (g of unit power second) divided by 101.97, change into ox second (SI of unit).For example, the numerical value of 33,947g power second is 332.9N (SI units).
Embodiment 1 (reference)
Between ring, there is the preparation of the organic radical hydrogen siloxane with at least two cyclosiloxane rings that contain SiH of short spacer
By in the presence of the Pt catalyzer, (a kind of siloxane reactions that on average has the dimethyl ethenyl blocking of 8 dimethyl siloxane units (DP=8), the preparation ring-type contains the siloxanes (it is the representative of component A) of SiH to make MeH ring bodies and VINYL SILOXANE#1.For three samples, specific [SiH]/[Vi] ratio remains on 3.0,3.42 and 4.0 times, and reacts under 40 ℃.Final polymkeric substance is the clear liquid with formula shown in the table 1.
Table 1: find that SiH content is respectively 0.374%, 0.432% and 0.505% in these siloxanes.
Table 1
Figure G2007800075754D00281
Embodiment 2 (reference)
There is the preparation of the organic radical hydrogen siloxane with at least two cyclosiloxane rings that contain SiH of long spacer
By in the presence of the Pt catalyzer, make MeH ring bodies and VINYL SILOXANE#2 (DP *=130) reaction, the ring-type for preparing the linear chain structure with the longer spacer of band contains the siloxanes (it is the representative of component A) of SiH.For three samples, [SiH]/[Vi] ratio is 3.0,3.42 and 4.0, and reacts under 40 ℃.Final SiH siloxanes is the clear liquid with object construction shown in the table 2.Find that SiH content is respectively 0.020%, 0.0240% and 0.0296%.In the organosilicon carrier fluid, obtain these siloxanes, to reduce final viscosity.
Table 2
Embodiment 3 (reference)
Preparation with organic radical hydrogen siloxane of at least two cyclosiloxane rings that contain SiH
By in the presence of the Pt catalyzer, make branched silicone or the reaction of methyl ethylene ring bodies of MeH ring bodies and dimethyl ethenyl blocking, prepare the siloxanes that the ring-type with branched structure contains SiH.The example of being derived by VINYL SILOXANE#3 in the presence of the Pt catalyzer has been shown in the table 3, its each in four side chains has about 30 dimethyl siloxane, amounts to about 120 dimethyl siloxane units (DP=120) thereby produce.For three samples, [SiH]/[Vi] ratio remains on 3.42 and 4.0 times, and reacts under 40 ℃.Use independently VINYL SILOXANE #4 to prepare component A).This SiH siloxanes is the clear liquid with structure of table 3 general introduction.SiH content is respectively 0.241%, 0.290% and 0.376%.
Table 3: the branching organic radical hydrogen siloxane of ring-type SiH siloxane blocking
Figure G2007800075754D00292
Figure G2007800075754D00301
Embodiment 4 (reference)
Preparation with organic radical hydrogen siloxane of at least two cyclosiloxane rings that contain SiH
By in reaction flask, mix MeH CYCLICS, VINYL SILOXANES (table 4 is listed) or 1,5-hexadiene and (if words of using) D5 as carrier fluid, preparation is with component A) the organic radical hydrogen siloxane that illustrates.Then, by adding the Pt (the Pt catalyst solution that contains 0.52wt%Pt) of 3-5ppm, this mixture of catalysis.Heat this mixture to 50 ℃, cause that the heat release hydrosilylation reactions occurs, then holding temperature is lower 3 hours at 50 ℃ to 70 ℃.Calculate the consumption of MeH CYCLICS and alkenyl compound, obtain 3.42 specific [SiH]/[Vi] ratio.Gained organic radical hydrogen siloxane is to have the average structure of table 4 general introduction and the clear liquid of performance.
Table 4
Embodiment # 4A 4B 4C 4D
React employed consumption
The MeH ring bodies, g 73.65 33.07 11.84 166.76
The alkenyl compound type VINYL SILOXANE #1 VINYL SILOXANE#5 VINYL SILOXANE#7 1,5-hexadiene
The alkenyl compound quality, g 126.35 166.93 228.11 33.24
D 5Fluid carrier, g 0 0 360.7 0
The Pt catalyzer, g 0.16 0.16 0.48 0.18
Stablizer, g 0 0 3.0 0.25
Total batch of material, g 200.16 200.16 604.13 200.43
The product outward appearance Limpid, low viscosity Limpid, low viscosity Limpid, modest viscosity Limpid, modest viscosity
Wt%[H] 0.4319 0.1939 0.0231 0.978
Mn,g/mol 3814 9131 22,167 1128
Mw,g/mol 18,688 78,303 39,103 1591
Embodiment 5 (reference)
A) have at least two organic radical hydrogen siloxane A that contain the cyclosiloxane ring of SiH) preparation
Use listed B component and as component MeH CYCLICS a), preparation ring-type as follows is with the additional examples of the siloxanes of S iH.
Table 5: ring-type SiH siloxanes
Embodiment # B component Remarks Wt%[H] Mn,g/mol Mw,g/mol
5A 1,5-hexadiene The SiH/ diene is 4.50, the former state preparation 1.06 418 770
5B 1,5-hexadiene The SiH/ diene is 4.50, VAP stablizer 1.06 415 760
5C Vinyl-Siloxane#5 The SiH/ vinyl is 3.42, VAP stablizer, prepares with 100% solid 0.4320
5D Vinyl-Siloxane#5 The SiH/ vinyl is 3.42, VAP stablizer, prepares with 100% solid 0.1939 9114 59590
5E Vinyl-Siloxane#6 The SiH/ vinyl is 3.42, VAP stablizer, prepares in the D5 fluid with 80% solid 0.1214 9721 36052
5F Vinyl-Siloxane#7 The SiH/ vinyl is 3.42, prepares the VAP stablizer in the D5 fluid with 40% solid 0.0231 14051 70697
5G Vinyl-Siloxane#7 The SiH/ vinyl is 4.0, prepares the VAP stablizer in the D5 fluid with 40% solid 0.0285 26284 66219
5H Vinyl-Siloxane#7 The SiH/ vinyl is 3.42, VAP stablizer, prepares in the D5 fluid with 50% solid 0.0289 29721 100166
5I Vinyl-Siloxane#8 The SiH/ vinyl is 4.0, VAP stablizer, prepares in the D5 fluid with 40% solid 0.0237 44482 203232
5J Viny1-Siloxane#1 The SiH/ vinyl is 3.42, VAP stablizer, prepares with 100% solid 0.4319 3658 8781
5K Vinyl-Siloxane#5 The SiH/ vinyl is 3.42, VAP stablizer, prepares with 100% solid 0.1939 7924 21167
Embodiment 6
Under the ratio of low [SiH]/[alkenyl], prepare silicone elastomer gels by ring-type SiH siloxanes
Under the ratio of low [SiH]/[alkenyl] 0.36, by make organic radical hydrogen siloxanes with at least two cyclosiloxane rings that contain SiH as component (A) and aliphatic unsaturated compound as component (B) reaction, the preparation silicone elastomer gels.In the D5 fluid the ring-type SiH siloxanes (under the ratio of the SiH/ alkenyl 3.42, preparing the siloxanes that this ring-type contains SiH by MeH-CYCLICS and VINYL SILOXANE #7) of embodiment 5 under 40% solid with in the D5 fluid and the VINYL SILOXANE#2 Isodecyl Neopentanoate (IDNP) hydrocarbon ester solvent in react.The gel that table 6 has been summarized this reaction and produced subsequently.
Table 6: in organic ester, at the silicone elastomer gels of low [SiH]/[alkenyl] than lower preparation
Embodiment # 6A 6B 6C
The ratio of [SiH]/[Vi] 0.361 0.361 0.361
Component A 5F 5F 5F
Remarks The SiH/ hexenyl is 3.42; 100dp siloxanes spacer; 40% solid in the D5 fluid The SiH/ hexenyl is 3.42; 100dp siloxanes spacer; 40% solid in the D5 fluid The SiH/ hexenyl is 3.42; 100dp siloxanes spacer; 40% solid in the D5 fluid
Wt%[H] 0.0231 0.0231 0.0231
B component Vinyl Siloxane #2 Vinyl Siloxane #2 Vinyl Siloxane #2
Carrier fluid The D5 fluid IDNP IDNP
%IEC 14.6 14.6 15.9
Actual amount Actual amount Actual amount Actual amount
The annular siloxane of embodiment 5F, g (40% solid in the D5 fluid) 26.82 26.85 20.51
Vinylsiloxane #2, g 33.18 33.2
Vinylsiloxane #9, g 39.52
The D5 fluid, g 240.0
IDNP,g 240.0 240.0
Platinum catalyst g (20 obtain 0.24g, 4.2ppm Pt) 0.24 0.24 0.24
Total batch of material, g 300.24 300.29 300.27
The gel outward appearance The gel that water-white is limpid; Firm annulus The gel that water-white is limpid The gel that water-white is limpid
Embodiment 7
The preparation silicone elastomer gels
As described in this embodiment, the low silicone elastomer gels of preparation elastomer content (EC).The lower preparation of D5 fluid (component (D)) silicone elastomer gels (embodiment 7A and 7C) at 3.0% elastic composition (component (A) and (B) sum) and 97%.In these embodiments, the average DP (polymerization degree) of siloxanes spacer is 100.
Table 7: the silicone elastomer gels that under low and moderate elastomer content, prepares
Embodiment # 7A 7B 7C
The ratio of SiH:Vi 0.90 0.90 0.90
Component A) Embodiment 5F Embodiment 5G Embodiment 5G
Remarks The SiH/ vinyl is 3.415; 100dp siloxanes spacer; 40% solid in the D5 fluid The SiH/ vinyl is 4.0; 100dp siloxanes spacer; 40% solid in the D5 fluid The SiH/ vinyl is 4.0; 100dp siloxanes spacer; 40% solid in the D5 fluid
At A) in SiH%, according to FTIR 0.0231 0.0231 0.0231
B component Vinyl Siloxane #9 Vinyl Siloxane #9 Vinyl Siloxane #8
The carrier fluid type D5 D5 D5
%IEC 3.0 20.0 3.0
Actual amount
Embodiment 5F, g (40% solid) 10.100
Embodiment 5G, g (40% solid, VAP stablizer) 59.39 6.70
Vinylsiloxane #2, g 4.987 36.268
Vinylsiloxane #8, g 6.34
The D5 fluid, g 285.0 204.5 287.0
Platinum catalyst g (20 obtain 0.24g, 4.2ppm) 0.24 0.24 0.24
Total batch of material, g 300.33 300.37 300.27
The gel outward appearance Shallow festucine limpid gel Shallow festucine limpid gel is firm Shallow festucine limpid, soft gel
Embodiment 8
The silicone elastomer gels that under the low elasticity body burden, prepares
Use the ring-type of relatively lacking spacer (i.e. low dp) to contain the siloxanes of SiH, prepare the silicone elastomer gels with low elasticity body burden.Below show the silicone elastomer gels by the SiH siloxanes preparation of embodiment 4C (spacer of 8dp) and embodiment 4D (spacer of 27dp).All gels in this embodiment have the elastomer content (being component (A) and summation (B)) of 5wt% and 95% D5 fluid (component (C)).
Table 8: the silicone elastomer gels that under low elastomer content, prepares
Embodiment # 8A 8B 8C
The ratio of [SiH]/[Vi] 0.90 0.90 0.90
Component A Embodiment 5C Embodiment 5D Embodiment 5D
Wt%[SiH] 0.430 0.190 0.190
B component Vinyl Siloxane#8 Vinyl Siloxane #2 Vinyl Siloxane #8
The carrier fluid type D5 D5 D5
%IEC 5.0 5.0 5.0
Actual amount Actual amount Actual amount Actual amount
Embodiment 5C siloxanes, g 0.420
Embodiment 5D siloxanes, g 1.351 0.902
Vinylsiloxane #2, g 13.660
Vinylsiloxane #8, g 14.586 14.080
The D5 fluid, g 285.0 285 285.0
Syl-Off4000, g (20 obtain 0.24g, 4.2ppm) 0.24 0.24 0.24
Total batch of material, g 300.25 300.25 300.22
The gel outward appearance Water-white limpid gel Water-white limpid gel Water-white limpid gel
Embodiment 9
Prepare the silicone elastomer blend by ring-type SiH siloxanes
Silicone elastomer blend (SEB) is the discrete crosslinked silicone elastomer gels particle that disperses in carrier fluid.SEB can serve as the organosilicon fluid effectively, and for example the rheology thickening material of D5 fluid is described as this embodiment.
In order to prepare the silicone elastomer blend, the known elastomer gel of original elastomer content (IEC) in the some above-described embodiments of mechanical shearing obtains little granularity, and further is diluted to required final elastomer content (FEC).For example, by machinery elastomer gel at intermittence, reduce granularity, then further dilute with the D5 fluid, obtain the final elastomer content (%FEC) of 10wt%, thereby preparation sample 9A is SEB.Final SEB is limpid thick gel paste, and its viscosity is about 676,000cps.Extra SEB has been shown in the table 9.Shown in these embodiment, observe the very high viscosity of these compositions of SEB in annular siloxane.
Table 9: the silicone elastomer blend of being derived by the elastomer gel of the siloxanes of endless belt SiH
Embodiment # 9A 9B 9C 9E 9F
Gelatinous composition
SiH (component (A)) Embodiment 5E, 37dp Embodiment 5H, 100dp Embodiment 5H, 100dp Embodiment 5H, 100dp Embodiment 5H, 100dp
Vinyl extender (component (B)) Vinyl Siloxane#2 Vinyl Siloxane#2 Vinyl Siloxane#2 Vinyl Siloxane#6 Vinyl Siloxane#7
Carrier fluid (component D) The D5 fluid The D5 fluid The D5 fluid The D5 fluid The D5 fluid
% IEC in elastomer gel 20 20 10 20 20
Diluted fluid The D5 fluid The D5 fluid The D5 fluid The D5 fluid The D5 fluid
%FEC in final SEB 10.0 10.0 10.0 10.0 10.0
The viscosity of SEB, cps 676,000 534,950 976,150 309,750 692,400
Embodiment 10
The embodiment of the pure silicone elastomer gels of preparation
In the situation that does not have carrier fluid to exist, the preparation silicone elastomer gels is shown in this embodiment.Component (A) and (B) sum represent elastomeric content and equal in these embodiments 100%.
In the presence of the Pt catalyzer, the siloxanes that is contained SiH by corresponding ring-type as component (A) and alkenyl official can compound as the hydrosilylation reactions of component (B), preparation silicone elastomer gels.Prepare the employed two kinds of ring-type SiH siloxanes of 100% silicone elastomer gels and be described in top embodiment 4J and the embodiment 4K those.With the hydrogen [SiH] of silicon bonding and the mol ratio of [alkenyl] be 0.90.The hardness that these silicone elastomer gels are measured by TextureAnalyzer is shown in table 10A and 10B.
Composition and the performance of the silicon gel of table 10A:100% elastomer content
Embodiment # 10A 10B 10C
Component (A) Embodiment 5K, the PDMS spacer of 8dp; The SiH/ alkenyl is 3.42 Embodiment 5K, the PDMS spacer of 8dp; The SiH/ alkenyl is 3.42 Embodiment 5K, the PDMS spacer of 8dp; The SiH/ alkenyl is 3.42
Component (B) Vinyl Siloxane #2 Vinyl Siloxane #8 VinylSiloxane#10
Component (D): carrier fluid type Nothing Nothing Nothing
In the gel [SiH]: the ratio of [alkenyl] 0.90 0.90 0.90
The % elastomer content 100.0 100.0 100.0
Solidification value 70℃ 70℃ 70℃
Actual amount
Component (A), g 7.98 5.41 3.19
Component (B), g 82.07 84.73 86.89
The Pt catalyzer, g 0.07 0.07 0.07
Total batch of material, g 90.12 90.21 90.15
The gel outward appearance Limpid, hard Limpid, hard Limpid, hard
The Texture Analyzer of gel, power 1, g 2617 2778 1902
Texture Analyzer, area F-T1:2, gs 10,959 13,434 9904
Gel hardness (compressive strength), N/m 2 2.02×10 5 2.15×10 5 0.147×10 5
By the gel viscosity that F-T1:2 derives, Ns/m 2 84.82×10 5 10.40×10 5 7.66×10 5
Composition and the performance of the silicon gel of table 10B:100% elastomer content
Embodiment # 10D 10E 10F
Component (A) Embodiment 5J, the PDMS spacer of 27dp; The SiH/ alkenyl is 3.42 Embodiment 5J, the PDMS spacer of 27dp; The SiH/ alkenyl is 3.42 Embodiment 5J, the PDMS spacer of 27dp; The SiH/ alkenyl is 3.42
Component (B) Vinyl Siloxane #6 Vinyl Siloxane #7 Vinyl Siloxane #2
Component (D): carrier fluid type Nothing Nothing Nothing
In the gel [SiH]: the ratio of [alkenyl] 0.90 0.90 0.90
%IEC 100.0 100.0 100.0
Solidification value, condition 70℃ 70℃ 70℃
Actual amount
Component (A), g 11.831 4.560 3.750
Component (B), g 78.19 85.49 86.264
The Pt catalyzer, g 0.08 0.08 0.08
Total batch of material, g 78.27 85.567 86.344
The gel outward appearance Limpid, hard Limpid, hard Limpid, hard
The Texture Analyzer of gel, power 1, g 6327 4131 3590
Texture Analyzer, area F-T1:2, gs 33947 21808 19391
Gel hardness (compressive strength), N/m 2 4.90×10 5 3.20×10 5 2.78×10 5
By the gel viscosity that F-T1:2 derives, Ns/m 2 26.28×10 5 16.88×10 5 15.01×10 5
By grinding/sheared gel, then dilute with selected carrier fluid (perhaps organosilicon fluid or organic solvent), prepare the silicone elastomer blend by the silicone elastomer gels of 100% elastomer content.
Embodiment 11
The hardness performance of selected silicone elastomer gels
According to above-described operation, prepare many silicone elastomer gels.Contained the siloxanes of SiH by selected ring-type as component (A), the compound of alkenyl official energy prepares these silicone elastomer gels as the D5 fluid of component (B) and surplus.Consumption should reaction for catalysis for the Pt catalyzer of the trace of about 4-10ppmPt.As shown in the table, change and the hydrogen [SiH] of silicon bonding and the mol ratio of [alkenyl].Under 50 ℃, carried out hydrosilylation reactions 4 hours.Formed gel in 15 minutes to 2 hours after in placing 50 ℃ of water-baths, this depends on its composition.
Use Texture Analyzer, characterize the hardness of the silicone elastomer gels of deriving." power 1 " is as shown above at the power reading of power with respect to the maximum point place of probe time of break-through curve.This power reading representative penetrates solidness or the hardness of middle gel at anti-probe.The second included performance is the reading of " power-time 1:2 area ".This is at the reading of maximum, force and the area integral between the time that passs (1 second in this case).This numerical value represents the elastic property of silicone elastomer gels.In these two kinds of performances, numerical value is higher, and gel hardness is larger.As illustrated, produce the silicone elastomer gels with wide region hardness.
Table 11: the gel hardness of various SEB
Silicone elastomer gels embodiment # Component (A): SiH type and structure Component (B) compound The ratio of [SiH]/[alkenyl] in the gel Power 1, g The area of power-time 1:2, gs Gel hardness, N/m 2 Gel viscosity, Ns/ m 2
11A 8dp spacer, SiH/ alkenyl are 3.42 130dp 0.80 230 1249 1.78 ×10 4 9.67 ×10 4
11B 8dp spacer, SiH/ alkenyl are 3.42 130dp 1.10 612 2844 4.74 ×10 4 22.01×10 4
11C 8dp spacer, SiH/ alkenyl are 3.42 130dp 1.30 600 3299 4.64 ×10 4 25.53×10 4
11D 8dp spacer, SiH/ alkenyl are 3.42 200dp 1.00 242 1307 1.87 ×10 4 10.12×10 4
11E Q-branching amounts to 120dp, at 3.42 times 200dp 0.95 149 806 1.15 ×10 4 6.24 ×10 4
11F C6 organic spacer base; The SiH/ alkenyl is 3.42 130dp 0.85 142 746 1.10 ×10 4 5.77 ×10 4
11G C6 organic spacer base; The siH/ alkenyl is 3.42 130dp 1.00 391 1919 3.03 ×10 4 14.85×10 4
11H C6 organic spacer base; The SiH/ alkenyl is 3.0 200dp 0.90 112 612 0.867×10 4 4.74 ×10 4
11I C6 organic spacer base; The siH/ alkenyl is 4.0 200dp 1.00 145 785 1.12 ×10 4 6.08 ×10 4
11J C6 organic spacer base; The siH/ alkenyl is 3.0 220dp; Q-branching 1.00 562 2671 4.35 ×10 4 20.67×10 4
11H (C6 organic/8dp is 50/50) that mixes is at 3.42 times 200dp 0.95 59 318 0.457×10 4 2.46 ×10 4
Embodiment 12
The hardness of the silicon gel of measuring by Texture Analyzer
Have the very elastomer gel of soft (soft gel) and the very elastomer gel of high rigidity reading (not yet illustrating) by controlling the elastomeric content of %, can preparing easily.Component (A) and (B) sum be elastomeric content, and can be up to 100%.In pure elastomeric situation, the hardness of this gel is very high, and can be processed into the product of powdery type, to obtain the powdery sensation.
As shown in table 12, by various components (A) and as the alkenyl official of component (B) can compound to prepare elastomer content be 10 to 20% gel.Dow Corning 245 fluids are as component (D).Production has the very soft gel of 4g power.On the other hand, can be by improving elastomer content wt%, by the very high gel of these component productivity readings.
Table 12: the silicon gel of different hardness
Silicone elastomer gels embodiment # Component (A): SiH type and structure Component (B): the dp of alkenyl compound The wt% of elastomerics (A)+(B) Power 1, g The area of power-time 1:2, gs Gel hardness, N/m 2 Gel viscosity, Ns/m 2
12A 27dp; The solid of preparation 80% in the D5 fluid 130dp 20.0 161 864 1.24×10 4 6.69×10 4
12B 27dp; The solid of preparation 80% in the D5 fluid 200dp 20.0 106 582 0.82×10 4 4.50×10 4
12C 37dp; The solid of preparation 80% in the D5 fluid 37dp 20.0 46 263 0.356×10 4 2.04×10 4
12D 37dp; The solid of preparation 80% in the D5 fluid 37dp 10.0 4 30 0.031×10 4 0.232×10 4
12E 37dp; The solid of preparation 80% in the D5 fluid 130dp 20.0 192 1037 1.49×10 4 8.03×10 4
12F 100dp; The solid of preparation 50% in the D5 fluid 130dp 20.0 139 780 1.08×10 4 6.04×10 4
12G 100dp; The solid of preparation 50% in the D5 fluid 130dp 10.0 29 171 0.224×10 4 1.32×10 4
12H 100dp; The solid of preparation 50% in the D5 fluid 100dp 20.0 194 1054 1.50×10 4 8.16×10 4
12I 100dp; The solid of preparation 50% in the D5 fluid 100dp 10.0 38 221 0.294×10 4 1.71×10 4
12J 100dp; The solid of preparation 50% in the D5 fluid 37dp 20.0 254 1403 1.97×10 4 10.86×10 4
12K 130dp; The solid of preparation 50% in the D5 fluid 200dp 20.0 101 565 0.782×10 4 4.37×10 4
Fig. 1 shows the gel for selected group of table 12, and the actual forces that is obtained by Texture Analyzer is with respect to the time of break-through curve of probe.
Embodiment 13
The additional examples of the SEB of preparation under low SiH/ vinyl ratio
Can under the SiH/ of the wide region vinyl ratio with under relative low SiH/ vinyl ratio, form elastomerics and gel.In order to set forth it, prepare following embodiment.
Component in this embodiment (A) is the organic radical hydrogen siloxane with 27dp siloxanes spacer that is similar to embodiment 5F, and it uses 3.4 SiH/ vinyl ratio preparation by MeH ring bodies and VINYL SILOXANE #5.
Embodiment # 13A 13B 13C 13D 13E 13F
The ratio of SiH:Vi 0.90 0.70 0.50 0.30 0.20 0.15
Component (B) VINYL SILOXANE#7 VINYL SILOXANE#7 VINYL SILOXANE#7 VINYL SILOXANE#7 VINYL SILOXANE#7 VINYL SILOXANE#7
Component (D) carrier fluid type Nothing Nothing Nothing Nothing Nothing Nothing
Actual amount
Component (A), g 8.41 6.70 4.90 3.01 2.03 1.54
Component (B), g 71.594 73.303 75.10 76.99 77.97 78.46
Syl-Off 4000,g(0.052%Pt) 0.05 0.05 0.05 0.05 0.05 0.05
Total batch of material, g 80.052 80.057 80.051 80.053 80.056 80.052
Gel/mixture outward appearance Limpid solid gel Limpid solid gel Limpid solid gel Limpid solid gel Limpid solid gel Limpid dumpable liquid does not form gel
Texture Analyzer, the power 1 of gel, g 3349 1749 491 44.3 3.0
Texture Analyzer, area F-T1:2, gs 18036 9136 2548 243 23.4
Gel hardness (compressive strength), N/m 2 25.9×10 4 13.5×10 4 3.80×10 4 0.343×10 4 0.023×10 4
According to the gel viscosity that F-T1:2 derives, Ns/m 2 13.96×10 5 7.07×10 5 1.97×10 5 0.188×10 5 0.018×10 5
Preparation: with the component (A) of predetermined amount with (B) be incorporated in the reaction vessel and mix, then the about 3.5ppm Pt catalyzer of introducing (is 0.05gDow CorningSyl-Off Pt solution, 0.52wt%Pt) when stirring.Under 70 ℃, carried out hydrosilylation reactions 3 hours.All mixtures gelling within 30 minutes heat-up time except embodiment 13F.Use Texture Analyzer to characterize gel hardness.
Embodiment 14 (Comparative Examples)
Comparative Examples: by straight chain MeH siloxanes/hexadiene chemical preparation silicone elastomer gels
With respect to the known silicone elastomer for thickening known in the art, US5 for example, 811,487 and US5, the thickening capabilities of those described in 880,210 is estimated thickening or the gelling ability of each SEB of the present invention.Use MD 94D ` 6MSiH polymkeric substance (MeH straight chain) and 1,5-hexadiene as carrier fluid, to provide 10.0 and the elastomer content of 5.0wt%, prepare two kinds of silicone elastomer blend compositions as chainextender and an amount of D5 fluid.Embodiment 8A obtains the weak and soft gel of water-white, but it is firm to be not so good as above-described embodiment 6A.Under 5.0% elastomer content, do not form gel or elastomerics in the composition of embodiment 8B.This embodiment shows the linear siloxanes base silicone elastomer with respect to this area routine, and ring-type of the present invention contains the improved thickening of siloxanes composition and the gel formation ability of SiH.
Table 8: compare silicone elastomer gels
Embodiment # 8A 8B
The ratio of [SiH]/[Vi] 0.90 0.90
The organic radical hydrogen siloxane The MeH straight chain The MeH straight chain
%SiH in the SiH polymkeric substance 0.068 0.068
Vinyl compound 1,5-hexadiene 1,5-hexadiene
The carrier fluid type D5 D5
%IEC 10.0 5.0
Solidification value/condition 50 50℃
Actual amount
The MeH straight chain, g 29.14 14.581
1,5-hexadiene, g 0.88 0.433
The D5 fluid, g 285.0 285.0
Platinum catalyst, g (20 obtain 0.24g, 4.2ppm) 0.24 0.24
Total batch of material, g 315.26 300.25
The gel outward appearance Water-white, very soft gel Water-white clear liquid, low viscosity
Embodiment 15
Preparation contains the silicone elastomer gels of activeconstituents
Contain the siloxanes (component A) of SiH by the ring-type with various chain structures, and as the aliphatic unsaturated compound of various structures and the type of component (B), preparation silicone elastomer gels.Calculate component (A) and consumption (B), [SiH] that obtains being scheduled to/[alkenyl] mol ratio, and in the gel that solidifies, be scheduled to the elastomer content of %.In forming the silicone elastomer gelation process, introduce 7.15wt%VAP to embodiment 15B and 15D, and be the representative of " preload method ".
Table 15
Embodiment # 15A 15B 15C 15D
Component (A): reference 4A 4A 4B 4B
Component (B): alkenyl compound VINYL SILOXANE#2 VINYL SILOXANE#2 VINYL SILOXANE#2 VINYL SILOXANE#2
The mol ratio of [SiH]/[alkenyl] 0.90 1.00 0.90 1.00
Component (C): carrier fluid D5 D5 D5 D5
Component (E): the wt%VAP in the gel 0.0 7.15 0.0 7.15
The gel outward appearance Limpid Limpid, glassy yellow Limpid Limpid, glassy yellow
Wt%IEC in the gel 20 20 20 20
The VITAMIN carrying method Preload Preload
Texture Analyzer, power 1, g 143 120 171 135
Texture Analyzer, power-time 1-2, gs 780 659 935 734
Gel hardness, N/m 2 11068 9288 13236 10449
Gel viscosity, Ns/m 2 60373 51088 72371 56813
According to following operation, preparation silicone elastomer gels in these embodiments:
1) it is interior and be stirred to even to Glass Containers (or reactor) to introduce all components except catalyzer;
2) this reaction mixture of catalysis (Pt of employing 3-5ppm) also places this mixture 70 ℃ the interior and continuation stirring of water-bath fast, until the time that spends when reaching gel state is recorded in the mixture gelling;
3) in 70 ℃ water-bath, keep reaction mixture vessel to amount to 4 hours.
Embodiment 16
Preparation contains the silicone elastomer gels of activeconstituents
Also being derived by the organic radical hydrogen cyclosiloxane of the different molecular structures shown in the embodiment of table 16 general introduction has and without the silicone elastomer gels of vitamin activity composition.As mentioned above, characterize the hardness of the silicone elastomer gels that contains the VAP activeconstituents by Texture Ana1yzer.Prepare gel according to embodiment 15 described operations.
Table 16
Embodiment # 16A 16B 16C 16D
Component (A): reference 4C 4C 4D 4D
Component (B): alkenyl compound VINYL SILOXANE#2 VINYL SILOXANE#2 VINYL SILOXANE#2 VINYL SILOXANE#2
The mol ratio of [SiH]/[alkenyl] 0.85 1.00 0.85 1.00
Component (C): carrier fluid D5 D5 D5 D5
Component (E): the wt%VAP in the gel 0.0 7.15 0.0 7.15
The gel outward appearance Limpid, firm gel Limpid, jonquilleous firm gel Limpid, firm gel Limpid, jonquilleous firm gel
Wt%IEC in the gel 20 20 20 20
The VITAMIN carrying method Preload Preload
Texture Analyzer, power 1, g 108 106 127 111
Texture Analyzer, power-time 1-2, gs 590 582 633 609
Gel hardness, N/m 2 8359 8205 9830 8592
Gel viscosity, Ns/m 2 45667 45048 48995 47138
Embodiment 17
The preparation silicone elastomer gels
Also being derived by the organic radical hydrogen cyclosiloxane with organic spacer base as shown in the embodiment of table 17 general introduction has and without the silicone elastomer gels of vitamin activity composition.Prepare gel according to embodiment 15 described operations.
Table 17
Embodiment # 17A 17B
Component (A): reference 4D 4D
Component (B): alkenyl compound VINYL SILOXANE#2 VINYL SILOXANE#2
Component (C): carrier fluid The D5 fluid The D5 fluid
The mol ratio of [SiH]/[alkenyl] in the gel 0.85 1.00
Component (D): vitamin activity ingredient w t% 0.00 7.15
The silicon gel outward appearance Limpid, yellow gel Limpid, yellow gel
Elastomerics % in the gel 20.0 20.0
The VITAMIN carrying method Preload
Texture Analyzer, power 1, g 142.0 103.5
Texture Analyzer, power-time 1-2, gs 746 566
Gel hardness, N/m 2 10991 8011
Gel viscosity, Ns/m 2 57742 43809
Embodiment 18
Preparation contains the silicone elastomer of activeconstituents
Summarized the operation of using embodiment 3 in the table 18, by the additional examples of the silicone elastomer gels of various organic radical hydrogen cyclosiloxane preparations.
Table 18
Embodiment # 18A 18B 18C 18D
Component (A): reference 4A 4A 4B 4B
Component (B): alkenyl compound VINYL SILOXANE#2 VINYL SILOXANE#2 VINYL SILOXANE#2 VINYL SILOXANE#2
Component (C): carrier fluid D5 D5 D5 D5
The mol ratio of [SiH]/[alkenyl] in the gel 0.90 1.00 0.90 1.00
Component (E): vitamin activity composition % 0.00 7.15 0.00 7.15
The silicon gel outward appearance Limpid, yellow gel Limpid, yellow gel Limpid, yellow gel Limpid, yellow gel
Elastomerics % in the gel 20.0 20.0 20.0 20.0
The VITAMIN carrying method Preload Preload
Texture Analyzer, power 1, g 130.6 148.0
Texture Analyzer, power-time 1-2, gs 711 803
Gel hardness, N/m 2 10109 11455
Gel viscosity, Ns/m 2 55033 62154
Embodiment 19
Preparation contains the silicone elastomer blend of activeconstituents
Be characterised in that the silicone elastomer gels composition with original elastomer content (IEC) by mechanical shearing, reduce granularity, dilute this mixture to required final elastomer content (FEC) with extra carrier fluid subsequently, prepare the silicone elastomer blend by several silicone elastomer gels.By using the Hauschild mixing tank, the mechanical shearing silicone gel composition, reduce granularity, then further with the dilution of Dow Corning 245 fluids, obtain final elastomer content (FEC) and be the silicone elastomer blend of 10wt%, thus the various silicone elastomer blends of general introduction in the preparation table 19.The silicone alloy composition of these embodiment contains VAP, wherein can comprise described VAP (embodiment 19B and 19D) with the preload method, perhaps obtain (embodiment 19A and 19C) by VAP being joined in the silicone gel composition by the back loading method.
Table 19
Embodiment # 19A 19B 19C 19D
Gel embodiment # reference 15A 15B 15C 15D
Component (C): carrier fluid The D5 fluid The D5 fluid The D5 fluid The D5 fluid
Component (E): the VAP wt% in SEB 3.53 3.58 3.53 3.58
The VITAMIN carrying method Back loading Preload Back loading Preload
Elastomerics wt% in SEB 10.0 10.0 10.0 10.0
The SEB outward appearance The smooth gel of limpid glassy yellow The smooth gel of limpid glassy yellow The smooth gel of limpid glassy yellow The smooth gel of limpid glassy yellow
The viscosity of SEB (under 10%FEC), cps 255000 342000 227000 677000
Embodiment 20
Preparation contains the silicone elastomer blend of activeconstituents
Table 20 has been summarized the operation of use embodiment 7 by the extra embodiment of the silicone elastomer blend of various silicone elastomer gels preparations.
Table 20
Embodiment # 20A 20B 20C 20D
Gel embodiment # reference 16A 16B 16C 16D
Component (C): carrier fluid The D5 fluid The D5 fluid The D5 fluid The D5 fluid
Component (E): the VAPwt% in SEB 3.53 3.58 3.53 3.58
The VITAMIN carrying method Back loading Preload Back loading Preload
Measure wt% in the elastomerics in SEB 10.0 10.0 10.0 10.0
The SEB outward appearance The smooth gel of limpid glassy yellow The smooth gel of limpid glassy yellow The smooth gel of limpid glassy yellow The smooth gel of limpid glassy yellow
The viscosity of SEB (under 10%FEC), cps 295000 1220000 43800 364000
Embodiment 21
Preparation contains the silicone elastomer blend of activeconstituents
Table 21 has been summarized the operation of use embodiment 19 by the extra embodiment of the silicone elastomer blend of various silicone elastomer gels preparations.
Use high performance liquid chromatography (HPLC), existence and the globality of checking VAP in SEB.The following details of summarizing the HPLC analytical technology.
The HPLC of Vitamin A Palmitate 1.7 M.I.U/Gram analyzes in SEB
The preparation of standard substance
By in hexane, generating the material solution of 1000ug/ml VAP, preparation standard thing.This is undertaken by measuring 107.2mg VAP and being introduced in the flask of volume 100ml.Then fill flask to the liquid level of 100ml with hexane.Then diluting this material solution is 4,40,100,300 and the solution of 500ug/ml to concentration.Use all standard substances of 4-1000ug/ml, the structural correction curve.
The SEB sample extraction
In this research, use two kinds of sample extraction methods.Use only hexane extraction PXL SEB sample.This adds 0.5g SEB and carries out in the 20g hexane by in bottle.Extract prescription sample (Sepigel and refreshing body water) by adding 1g prescription sample and 10gTHF:IPA (1:1).Then sample is placed on the wobbler of wrist effect and mixed 2 hours.After finishing mixing, use 0.45 micron PTFE strainer, filtered sample is in the HPLC bottle.
The HPLC condition
In one of two HPLC systems: be furnished with the Waters 600EHPLC of Waters 991 PDA detectors, or be furnished with the analysis of carrying out VAP of the present invention on the Waters 2695 Separations devices of Waters 2996 PDA detectors.Post and post protection equipment (column guard) are the Novapak Cl 8 available from Waters.Heat the steady temperature of this post to 35 ℃.Moving phase is 45% methyl alcohol, 20% vinyl cyanide and 35% Virahol that is set under the flow velocity 1ml/min.Inject each sample of 10ul and allow running 12 minutes.The PDA detector is set as the wavelength of 325nm.
Table 21
Figure G2007800075754D00471
Embodiment 22
Preparation contains the silicone elastomer blend of activeconstituents
Table 22 has been summarized the operation of use embodiment 19 by the extra embodiment of the silicone elastomer blend of various silicone elastomer gels preparations.
Use high performance liquid chromatography (HPLC), utilize the operation of general introduction among the embodiment 21, existence and the globality of checking VAP activeconstituents in SEB.
Table 22
Embodiment 23
Preparation does not have the silicone elastomer gels that contains activeconstituents of carrier fluid
Use the operation of embodiment 15, in the situation of not adding any carrier fluid (component C), by various organic radical hydrogen cyclosiloxane, the preparation silicone elastomer gels.Summarized the performance of prescription and gained gel in the table 23.
Table 11A
Embodiment # 23A 23B 23C
Component (A): reference 4A 4A 4A
Component (B): alkenyl extender type VINYL SILOXANE#2 VINYL SILOXANE#8 VINYL SILOXANE#10
Component (C): carrier fluid type Nothing Nothing Nothing
Component (E): activeconstituents type and wt% Vitamin A Palmitate 1.7 M.I.U/Gram; 5% Vitamin A Palmitate 1.7 M.I.U/Gram; 5% Vitamin A Palmitate 1.7 M.I.U/Gram; 5%
The ratio of [siH]/[alkenyl] in gel 0.95 0.95 0.95
Elastomer content % 95.0 95.0 95.0
Solidification value/condition 70℃ 70℃ 70℃
Actual amount
Component (A), SiH, g 7.99 5.29 3.16
Component (B), alkenyl extender, g 77.58 80.23 82.37
Component (D), and the Pt catalyzer (0.52%, Syl-Off4000), g 0.068 0.068 0.068
The Vitamin A Palmitate 1.7 M.I.U/Gram of component (E): 98.5/1.5/BHT mixture, g 4.57 4.55 4.57
Total batch of material, g 90.21 90.14 90.17
The gel outward appearance Light yellow emulsus Light yellow emulsus Light yellow emulsus
Texture Analyzer, the power 1 of gel, g 2916 1660 1330
Texture Analyzer, power-time 1-2, gs 15847 8974 7233
Gel hardness, N/m 2 225704 128487 102944
Gel viscosity, Ns/m 2 1226586 694604 559847
Table 23B
Embodiment # 23D 23E 23F
Component (A): SiH PXL type and structure 4B 4B 4B
Component (B): alkenyl extender type Vinyl Siloxane#6 Vinyl Siloxane#7 Vinyl Siloxane#2
Component (C): carrier fluid type Nothing Nothing Nothing
Component (E): activeconstituents type and wt% Vitamin A Palmitate 1.7 M.I.U/Gram; 5% Vitamin A Palmitate 1.7 M.I.U/Gram; 5% Vitamin A Palmitate 1.7 M.I.U/Gram; 5%
The ratio of [SiH]/[alkenyl] in the gel 0.90 0.90 0.90
%IEC 100.0 100.0 100.0
Solidification value/condition 70℃ 70℃ 70℃
Actual amount
Component (A), SiH PXL, g 11.776 4.510 3.755
Component (B), alkenyl extender, g 73.14 80.99 81.77
Component (D), Pt catalyzer (0.52%, Syl-Off 4000), g 0.068 0.068 0.068
The Vitamin A Palmitate 1.7 M.I.U/Gram of component (E): 98.5/1.5/BHT mixture, g 4.57 4.58 4.56
Total batch of material, g 89.55 90.15 90.15
Gel outward appearance Texture Analyzer, the power 1 of gel, g Texture Analyzer, power-time 1-2, gs gel hardness, N/m 2Gel viscosity, Ns/m 2 Limpid yellow firm gel 5,667 30,940 438,636 2394811 almost Muddy to opaque yellow firm gel 2,744 14,847 212,390 1149184 The opaque light yellow gel 3,658 19,835 283,136 1535264 of emulsus

Claims (23)

1. gelatinous composition, it comprises the silicone elastomer that is obtained by the following substances reaction:
A) in its molecule, have at least two organic radical hydrogen siloxanes that contain the cyclosiloxane ring of SiH,
B) in its molecule, have the compound of at least two aliphatic unsaturated groups or the mixture of compound,
C) hydrosilylation catalysts,
D) optional carrier fluid, and
E) personal care or health care activeconstituents.
2. the composition of claim 1, wherein the general formula of organic radical hydrogen siloxane is G-[Y-G] a, wherein G is the cyclosiloxane that contains at least one SiH unit, and Y is divalent organic group, and a is greater than 0.
3. claim 1 or 2 composition, wherein the organic radical hydrogen siloxane is the hydrosilylation reactions preparation by following substances:
A) have the organic radical hydrogen cyclosiloxane of at least two SiH unit at the siloxanes ring,
B) in its molecule, have the compound of at least two aliphatic unsaturated groups or the mixture of compound,
Wherein the molar ratio range of SiH unit and unsaturated group is 2/1-8/1.
4. the composition of claim 3, wherein the general formula of organic radical hydrogen cyclosiloxane is [(CH 3) HSiO] g, wherein g is 3-8.
5. claim 1 or 2 composition, wherein B) to be selected from general formula be R for the compound that has at least two aliphatic unsaturated groups in its molecule 2-Y-R 2Compound, R wherein 2Be unit price unsaturated aliphatic group, and Y is bivalent hydrocarbon radical, siloxanes, polyoxy alkylidene or its mixture.
6. claim 1 or 2 composition, the compound that wherein has at least two aliphatic unsaturated groups are selected from that to contain general formula be R 2R mSiO (4-m)/2The organopolysiloxane of at least two siloxane units, wherein R is organic group, R 2Be unit price unsaturated aliphatic group, and m is 0-3.
7. the composition of claim 6, wherein the general formula of organopolysiloxane is:
(R 2R 2SiO 0.5)(SiO 2) w(R 2R 2SiO 0.5),
(R 2R 2SiO 0.5)(SiO 2) w(R 2SiO) x(R 2R 2SiO 0.5),
(R 2R 2SiO 0.5)(R 2SiO) x(R 2R 2SiO 0.5),
(R 3SiO 0.5)(R 2SiO) x(R 2RSiO) y(R 3SiO 0.5),
(R 3SiO 0.5) (R 2SiO) x(R 2RSiO) y(RSiO 1.5) z(R 3SiO 0.5), or
(R 3SiO 0.5)(R 2SiO) x(R 2RSiO) y(SiO 2) w(R 3SiO 0.5)
W 〉=0 wherein, x 〉=0, y 〉=2 and z 〉=0, R is organic group, and
R 2It is unit price unsaturated aliphatic group.
8. the composition of claim 7, wherein R is methyl and R 2CH 2=CH-or CH 2=CH-(CH 2) 4-.
9. the composition of claim 8, wherein organopolysiloxane be have the vinyl functional of following average formula or hexenyl official can polydimethylsiloxane:
CH 2=CH(Me) 2SiO[Me 2SiO] xSi(Me) 2CH=CH 2
CH 2=CH-(CH 2) 4-(Me) 2SiO[Me 2SiO] xSi (Me) 2-(CH 2) 4-CH=CH 2, or
Me 3SiO[(Me) 2SiO] x[CH 2=CH(Me)SiO] ySiMe 3
Wherein Me is methyl, x 〉=0, y 〉=2.
10. the composition of claim 1, wherein C) hydrosilylation catalysts is the catalyzer of platinum group.
11. the composition of claim 1, wherein A)/B) mol ratio is 10/1-1/10.
12. the composition of claim 1, wherein carrier fluid is to be 1-1000mm at 25 ℃ of lower range of viscosities 2The siloxanes of/s or organic fluid.
13. the composition of claim 1, wherein carrier fluid is decamethylcyclopentaandoxane, Permethyl 99A. or Isodecyl Neopentanoate.
14. the composition of claim 1, wherein E) be the personal care activeconstituents that is selected from VITAMIN, sun-screening agent, plant milk extract or spices.
15. the composition of claim 1, wherein E) be the health care activeconstituents that is selected from part drug's activeconstituents, protein, enzyme, anti-mycotic agent or biocide.
16. the composition of claim 1, wherein component E) be Vitamin A Palmitate 1.7 M.I.U/Gram.
17. the composition of claim 1, wherein component E) be octyl methoxycinnamate.
18. the composition of claim 2, wherein Y is divalence siloxanes, divalence polyoxy alkylidene or its combination.
19. a method for preparing the silicone elastomer gels that contains activeconstituents, the method comprises:
I) make the following substances reaction:
A) have the organic radical hydrogen cyclosiloxane of at least two SiH unit at the siloxanes ring,
B) in its molecule, have the compound of at least two aliphatic unsaturated groups,
C) hydrosilylation catalysts
Form:
A) in its molecule, have at least two organic radical hydrogen siloxanes that contain the cyclosiloxane ring of SiH,
The molar ratio range of the aliphatic unsaturated group SiH unit and the B component of component in a) wherein) is 2/1-8/1,
II) at D) in the presence of the optional carrier fluid, further make:
A) in its molecule, have at least two organic radical hydrogen siloxanes that contain the cyclosiloxane ring of SiH, with extra consumption
B) in its molecule, have the compound of at least two aliphatic unsaturated groups,
C) hydrosilylation catalysts
Reaction forms silicone elastomer gels,
III) mix E) personal care or health care activeconstituents and silicone elastomer gels, form the silicone elastomer gels that contains activeconstituents.
20. a method for preparing the silicone elastomer gels that contains activeconstituents, the method comprises:
I) make the following substances reaction:
A) have the organic radical hydrogen cyclosiloxane of at least two SiH unit at the siloxanes ring,
B) in its molecule, have the compound of at least two aliphatic unsaturated groups,
C) hydrosilylation catalysts
Form:
A) in its molecule, have at least two organic radical hydrogen siloxanes that contain the cyclosiloxane ring of SiH,
The molar ratio range of the aliphatic unsaturated group SiH unit and the B component of component in a) wherein) is 2/1-8/1,
II) at D) optional carrier fluid, under E) personal care or health care activeconstituents exist, further make:
A) in its molecule, have at least two organic radical hydrogen siloxanes that contain the cyclosiloxane ring of SiH, with extra consumption
B) in its molecule, have the compound of at least two aliphatic unsaturated groups,
C) hydrosilylation catalysts
Reaction forms the silicone elastomer gels that contains activeconstituents.
21. according to claim 19 or 20 the preparation silicone elastomer gels.
22. a method for preparing the gel paste composition, the method comprises:
I) shear the silicone elastomer gels of claim 1 or 21,
II) in conjunction with the silicone elastomer gels of this shearing and the D of additional quantity) carrier fluid, form the gel paste composition.
23. the gel paste composition of the preparation of method according to claim 22.
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