CN102488625B - Benzophenone-type chemical sun-screening agent-coated polysiloxane composite particle and preparation method thereof - Google Patents
Benzophenone-type chemical sun-screening agent-coated polysiloxane composite particle and preparation method thereof Download PDFInfo
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- CN102488625B CN102488625B CN201110439641.3A CN201110439641A CN102488625B CN 102488625 B CN102488625 B CN 102488625B CN 201110439641 A CN201110439641 A CN 201110439641A CN 102488625 B CN102488625 B CN 102488625B
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Abstract
The invention discloses a benzophenone-type chemical sun-screening agent-coated polysiloxane composite particle and a preparation method thereof. The preparation method comprises the following steps of uniformly dispersing an oil phase comprising a benzophenone-type chemical sun-screening agent, an emulsifier, oil and one or more auxiliary emulsifiers, homogenizing a water phase with addition of the oil phase, carrying out homogenization stirring, cooling to a room temperature to obtain benzophenone-type chemical sun-screening agent-containing nano-emulsion, preparing an organosilicon monomer hydrolysate solution, mixing the organosilicon monomer hydrolysate solution and the benzophenone-type chemical sun-screening agent-containing nano-emulsion, adjusting a pH value of the mixture to a pH value of 7.5 to 13.5, treating the mixture having a pH value of 7.5 to 13.5 at a temperature of 0 to 100 DEG C at a rotating rate of 10 to 1000r/min for 0.1 to 24 hours to obtain benzophenone-type chemical sun-screening agent-coated polysiloxane composite particle suspension, and carrying out washing, centrifugal separation and drying to obtain the benzophenone-type chemical sun-screening agent-coated polysiloxane composite particles. The preparation method provided by the invention has simple processes, high yield and good industrial production prospects.
Description
Technical field
The present invention relates to a kind of coated chemical sun polysiloxane composite particles, more particularly relate to polysiloxane composite particles of the chemical sun that a kind of coated Benzophenones thing is formed and preparation method thereof.
Background technology
Chemical sun mainly refers to the organic compound with the ultraviolet radiation that can be absorbed with injury effect, is commonly referred to chemical ultraviolet absorbent., UV(ultraviolet different according to the wave band of protection radiation) absorbent can be divided into UVA(life ultraviolet) and UVB(open air ultraviolet) two kinds of absorbent.Chemically structure can be divided into para-amino benzoic acid and esters, salicylic acid esters and derivant thereof, o-aminobenzoa class, benzophenone and derivant, p-methoxycinnamic acid class, methane derivative and camphor derivative etc.Be applied to chemical sun in cosmetics due to its photo-labile and the zest to skin, can produce certain side effect, belong at European Union's part sunscreen and limit the use of raw material, part sunscreen then belongs to forbidding raw material.Meanwhile, general sunscreen only has anti-sunlight function in a kind of wavelength band of UVA or UVB wave band.
Benzophenones chemical ultraviolet absorbent can absorb the radiation in UVB and UVA district, but its absorbance is slightly poor, and structural formula is:
In structure above:
Oxybenzone (Benzophenone-3): R
1=OH, R
2=OCH
3, R
3=R
4=R
5=H
2,2 '-dihydroxy-4-methoxy benzophenone (Benzophenone-8): R
1=OH, R
2=OCH
3, R
3=R
4=H, R
5=OH
2-hydroxyl-4-methoxy benzophenone-5-sulfonic acid (Benzophenone-4): R
1=OH, R
2=OCH
3, R
3=SO
3, R
4=H
2,4 '-dihydroxy benzophenone (Benzophenone-1): R
1r
2=OH, R
3=R
4=R
5=H
2,2', 2,4 '-tetrahydroxybenzophenone (Benzophenone-2): R
1r
2=R
4=R
5=OH, R
3=H
2,2 '-dihydroxy-4,4 '-dimethoxybenzophenone (Benzophenone-6): R
1=R
5=OH, R
2=R
4=OCH
3, R
3=H
2-hydroxyl-4-N-ethylhexyl benzophenone (Benzophenone-12): R
1=OH, R
2=OC
8h
17(iso), R
3=R
4=R
5=H.
This compounds all contains the substituent group of ortho position and para-position, and some also containing two ortho-substituent, can generate intramolecular hydrogen bond like this, electron delocalization effect is easier to occur, corresponding energy demand also reduces therewith, and maximum absorption wavelength moves to long wave direction, is in UVA scope.The existence of ortho position and para-orientating group, form this compounds and have two absworption peaks, para-orientation causes UVB to absorb, and ortho position replacement causes UVA to absorb.
Organosilicon microsphere is that organosilane monomers carries out polyreaction under certain conditions and obtains.The characteristics such as organosilicon microsphere has that hardness is high, fusing point is high, wear-resisting, lubricious, nontoxic, tasteless, transparent, gloss, and Stability Analysis of Structures, environmental friendliness, is therefore widely used as filler and the modifier of rubber, plastics, cosmetics, coating etc.In recent years, the research and development of organosilicon microsphere are one of focuses of organosilicon material research.
Current domestic disclosed relevant core-shell type polysiloxane composite particles, but there is not yet the Silicone particles of the chemical sun that openly coated Benzophenones is formed, difference of the present invention is mainly first to form the nanoemulsions comprising the chemical sun that Benzophenones is formed, and carries out siloxanes hydrolysis more afterwards, polycondensation forms coated shell; And the nano polysilicon oxygen alkane compound particle stable performance of the chemical sun that the distinctive stability of Silicone particles makes prepared coated Benzophenones be formed, in application system, substantially increase the stability of the chemical sun that Benzophenones is formed.
Summary of the invention
An object of the present invention is the polysiloxane composite particles in order to the chemical sun providing a kind of coated Benzophenones to be formed.
Two of object of the present invention is to provide the preparation method of the polysiloxane composite particles of the chemical sun that above-mentioned a kind of coated Benzophenones is formed.
Technical scheme of the present invention
A polysiloxane composite particles for the chemical sun that coated Benzophenones is formed, prepare by the following method:
(1) preparation of the nanoemulsions of the chemical sun that Benzophenones is formed, is comprised
Calculate by mass percentage, described comprise the nanoemulsions of the chemical sun that Benzophenones is formed raw material composition and content as follows:
Sunscreen 0.1 ~ 10%
Emulsifying agent 0.1 ~ 20%
Oils and fats 0.1 ~ 10%
Help Emulsion 0.1 ~ 20%
Surplus is water;
The above-mentioned nanoemulsions preparation process comprising the chemical sun that Benzophenones is formed is as follows:
First chemical sun Benzophenones formed, emulsifying agent, oils and fats and help being uniformly mixed of Emulsion, then while homogenizing water, the chemical sun that Benzophenones is formed, emulsifying agent, oils and fats and help the mixture being uniformly mixed gained of Emulsion to be added to the water, continue homogenizing, it is 10000 ~ 50000r/min that homogenizing process controls homogenizing speed, time is 0.1 ~ 30min, after homogenizing, stirring is cooled to room temperature and namely obtains the nanoemulsions comprising the chemical sun that Benzophenones is formed, described whipping process controls mixing speed 10 ~ 1000r/min,
The chemical sun that described sunscreen is formed for Benzophenones;
The chemical sun that described Benzophenones is formed is benzophenone-1, one or more mixture formed in benzophenone-2, OXYBENZONE, UVNUL MS-40, benzophenone-5, benzophenone-6 and Benzophenone-9;
Described emulsifying agent is anion surfactant or non-ionic surface active agent;
Wherein said anion surfactant is fatty alcohol sulfate salt, and its molecular formula is C
nh
2n+1sO
4m, wherein n is 11 ~ 17, M is Na, K or NH
3;
Described non-ionic surface active agent is poly alkyl alcohol glyceride series, be four polyglycereol monostearates, four polyglycereol five stearates, four polyglycerol monooleate, four polyglycereol five oleates, four polyglycereol monolaurates, six polyglycereol monostearates, six polyglycereol five stearates, six polyglycerol monooleate, six polyglycereol five oleates, six polyglycereol monolaurates, eight polyglycereol monostearates, eight polyglycereol eight stearates, eight polyglycerol monooleate, eight polyglycereol monolaurates, ten polyglycereol monostearates, ten polyglycereol five stearates, ten polyglycerol monooleate or ten polyglycereol monolaurates,
Described oils and fats be mineral grease, natural origin Vegetable oil lipoprotein, natural origin animal oil and synthetic ester oil one or more rich mixture,
Described mineral grease is white oil, ceresine or microwax;
Described natural origin Vegetable oil lipoprotein is olive oil, palm-kernel oil, American Avocado Tree oil, soybean oil, Testa oryzae oil, Apricot kernel oil, Oleum helianthi, Camellia oil, cocoa butter, mother-in-law sieve's fat, mowrah fat, Adeps Bovis seu Bubali resin, Brazil wax or aromatic wax;
Described natural origin animal oil is returned student's oil, Adeps Serpentis, horse fat, exquisite Adeps Cervi or spermaceti;
Described synthetic ester oil is type siloxane oils and fats, as cured in methyl polysiloxane, methyl phenyl silicone, Methyl Hydrogen Polysiloxane Fluid, polyether modified silicon oil, long chain alkyl modified silicon oil, cyclic polysiloxanes, amino-modified silicone oil, Carboxyl Modified Polydimethylsiloxane, methyl polysiloxane emulsion, organosilicon or silicones;
Described co-emulsifier is monohydric alcohol or polyhydric alcohol, and wherein the molecular formula of monohydric alcohol is C
nh
2n+1oH, wherein n is between 1 ~ 12; Polyhydric alcohol is ethylene glycol, 1,2-PD, 1,3-PD, 1, one or more mixed alcohols formed in 3 butanediols, propylene carbonate and glycerol;
(2), the preparation of organic silicon monomer hydrolysising product solution
Organosilicon is added in the mixture of water and/or organic solvent, then under acid or alkali effect, control pH be 1 ~ 6 or pH 7.5 ~ 11.5 to be hydrolyzed reaction, hydrolysis time, at 0.1 ~ 10h, is preferably 2 ~ 4.5h, temperature 1 ~ 100 DEG C, be preferably 15 ~ 30 DEG C, mixing speed 10 ~ 1000r/min, is preferably 60 ~ 100r/min, obtains organic silicon monomer hydrolysising product solution after having reacted;
Described organosilyl addition calculates i.e. organosilicon in mass ratio: the mixture of water and/or organic solvent is 1 ~ 50:100;
Described organosilicon is organosiloxane, and its structural formula is R
1nSiX
(4-n);
Wherein R
1that representative is selected from replacement or the unsubstituted univalent perssad having a C atom to be connected directly between alkyl on Si atom or alkenylphenyl, n is the integer of 0 ~ 3, X is hydrolysising group, is hydroxyl, hydrogen, alkoxyl, halogen group, carboxyl, amino or siloxy;
As n > 1, each R1 group can be identical or different;
And as (4-n) > 1, each X group can be identical or different;
Described acid is one or more mixed acid in citric acid, acetic acid, oxalic acid, tartaric acid, hydrochloric acid, phosphoric acid, carbonic acid and sulfurous acid;
Described alkali is one or more mixed bases in sodium carbonate, sodium bicarbonate, sodium hydroxide, potassium hydroxide, ammonia, methylamine, dimethylamine, ethamine, diethylamine and triethylamine;
Said organic solvent is methanol, ethanol, ethylene glycol, propanol, isopropyl alcohol, butanols, isobutanol, propylene carbonate, glycerol, Methanamide, N, one or more mixture in N-dimethyl acetylamide, DMF, acetone, oxolane, dimethylsulfone, ethyl acetate, pyridine and acetonitrile;
(3) preparation of the nano polysilicon oxygen alkane compound particle suspension of the chemical sun, formed containing coated Benzophenones
The organic silicon monomer hydrolysising product solution obtain step (2) and the nanoemulsions comprising the chemical sun that Benzophenones is formed of step (1) gained calculate in mass ratio, namely the nanoemulsions of the chemical sun that Benzophenones is formed is comprised: organic silicon monomer hydrolysising product solution is that 0.1:99.9 ~ 50:50 mixes, then with alkaline matter regulate pH be carry out polycondensation reaction under the condition of 7.5 ~ 13.5 after obtain the suspension of the polysiloxane composite particles comprising coated Benzophenones or derivatives thereof chemical sun, it is 0 DEG C ~ 100 DEG C that polycondensation process controls reaction temperature, be preferably 5 ~ 25 DEG C, rotating speed is 10 ~ 1000r/min, be preferably 100 ~ 150r/min, time is 0.1 ~ 24h, be preferably 5h,
The suspension of the polysiloxane composite particles of chemical sun will formed containing coated Benzophenones after polycondensation reaction completes, with water, ethanol circulation cleaning 3 times, and control centrifugal rotational speed 10000r/min ~ 15000 r/min carry out centrifugal, filter after 10min ~ 100min, filter cake dry 5 ~ 10h at 100 ~ 200 DEG C of gained, the solids finally obtained are the polysiloxane composite particles of the chemical sun that nano level coated Benzophenones is formed;
Wherein said alkaline matter is sodium carbonate, sodium bicarbonate, sodium hydroxide, potassium hydroxide, ammonia, methylamine, dimethylamine, ethamine, diethylamine or triethylamine.
The polysiloxane composite particles of the chemical sun that a kind of coated Benzophenones of the present invention is formed, is suitable for being applied in sunscreen product, as the articles for use such as sun care preparations, sun-screening umbrella.
Simultaneously, in order to avoid the permeability of chemical sun on skin that Benzophenones is formed, the particle diameter of lipid particles is not easily too little, the particle diameter of the polysiloxane composite particles of the chemical sun formed by the coated Benzophenones of gained of the present invention between 80nm ~ 500nm, preferred 100nm ~ 300nm.The polysiloxane composite particles of the chemical sun that the coated Benzophenones of gained is formed.
Beneficial effect of the present invention
The polysiloxane composite particles of the chemical sun that a kind of coated Benzophenones of the present invention is formed, comprise the nanoemulsions of the chemical sun that Benzophenones is formed owing to first being formed in preparation process, carry out siloxanes hydrolysis more afterwards, polycondensation forms coated shell; The polysiloxane composite particles performance of the chemical sun that the distinctive stability of such Silicone particles makes prepared coated Benzophenones be formed is more stable, substantially increases the stability of the chemical sun that Benzophenones is formed in application system.
And the polysiloxane composite particles of the chemical sun formed due to a kind of coated Benzophenones of the present invention is coated in Silicone particles by comprising the chemical sun that Benzophenones formed, thus avoid and contact with the direct of skin, greatly reduce chemical sun that Benzophenones formed to the zest of skin.Good sun-proof result can be embodied.
In addition, the polysiloxane composite particles of the chemical sun that a kind of coated Benzophenones of the present invention is formed, owing to being comprise the nanoemulsions of the chemical sun that Benzophenones is formed, organosilicon as raw material, therefore preparation method is easy, and productive rate is high, there is industrial production prospect.
Detailed description of the invention
Below by embodiment, the present invention is set forth further, but do not limit the present invention.
embodiment 1
A nano polysilicon oxygen alkane compound particle for the chemical sun that coated OXYBENZONE is formed, prepare by the following method:
(1) preparation of the nanoemulsions of the chemical sun that OXYBENZONE is formed, is comprised
The described nanoemulsions comprising the chemical sun that OXYBENZONE is formed is calculated by mass percentage, its raw material composition and content as follows:
Sunscreen 5%
Emulsifying agent 5%
Oils and fats 5%
Help Emulsion 5%
Surplus is water;
The chemical sun that described sunscreen is formed for OXYBENZONE, the product that ISP International Specialty Products company limited produces;
Described emulsifying agent is six polyglycereol monostearates, and Lonza(dragon is husky) emulsifying agent for cosmetics of Chemical Co., Ltd.;
Described oils and fats is American Avocado Tree oil, lipo(Lai Baokang) daily use chemicals (Shanghai) Co., Ltd. produce product;
Described co-emulsifier is the grade product of propylene glycol, traditional Chinese medicines group;
The above-mentioned nanoemulsions preparation process comprising the chemical sun that OXYBENZONE is formed is as follows:
First chemical sun OXYBENZONE formed, emulsifying agent, oils and fats and help being uniformly mixed of Emulsion, the chemical sun that OXYBENZONE is formed, emulsifying agent, oils and fats and help the mixture being uniformly mixed gained of Emulsion and water to be heated to 60 ~ 80 DEG C respectively; The chemical sun while homogenizing water, OXYBENZONE formed, emulsifying agent, oils and fats and help the mixture being uniformly mixed gained of Emulsion to be added to the water, proceed homogenizing, homogenizing process control rate is 10000r/min, time is 3min, stir the nanoemulsions being cooled to room temperature and must comprising the chemical sun that OXYBENZONE is formed after homogenizing, above-mentioned whipping process controls mixing speed 100r/min;
(2), the preparation of organic silicon monomer hydrolysising product solution
8g trimethylmethoxysilane is placed in 92g water and alcohol mixeding liquid, water: ethanol is 1:99, with hydrochloric acid solution by pH regulator to 3.0 ~ 4.0, be hydrolyzed reaction, hydrolysis time is 4h, temperature 15 DEG C, mixing speed 60r/min, obtains organic silicon monomer hydrolysising product solution after having reacted;
(3) preparation of the suspension of the nano polysilicon oxygen alkane compound particle of the chemical sun, formed containing coated Benzophenones and derivant thereof
Organic silicon monomer hydrolysising product solution 70g step (2) obtained mixes with the nanoemulsions 30g comprising the chemical sun that OXYBENZONE is formed of step (1) gained, then pH is regulated to be 7.5 ~ 8.5 with ammonia, control temperature is 10 DEG C, mixing speed is 100 r/min, obtains the suspension of the polysiloxane composite particles of the chemical sun formed containing coated OXYBENZONE after time 5h;
By the suspension containing the polysiloxane composite particles of the chemical sun that coated OXYBENZONE is formed of gained, with water, ethanol circulation cleaning 3 times, and centrifugal, filtration, dry 10h at 100 DEG C, obtain the polysiloxane composite particles of the chemical sun that the nano level coated OXYBENZONE of 11.6g is formed, its particle diameter is 0.8 μm.
The sun-proof performance of the polysiloxane composite particles of the chemical sun formed with the nano level coated OXYBENZONE of ultraviolet spectrophotometry to above-mentioned gained measures, this mensuration adopts the evaluation methodology-ultraviolet spectrophotometry of GB QB/T2410-98 sun-proof performances to measure, and the present invention's spectrophotometric used is counted Shanghai precision scientific instrument company and manufactured 759 ultraviolet spectrophotometers.Determination step is as follows:
(1), by the breathable adhesive tape that 3M company produces be cut into lcm × 4cm size, be pasted onto quartz colorimetric utensil printing opacity and survey on the surface;
(2), switch on power, preheating spectrophotometer, setting UVB district determined wavelength is 280nm, 290nm, 300nm, 310nm and 320nm, and UVA district determined wavelength is 330nm, 340nm, 350nm, 360nm, 370nm, 380nm, 390nm and 400nm;
(3), by the quartz colorimetric utensil posting adhesive tape sample arm and reference light paths is placed in, adjustment instrument zero;
(4), get powder sample prepared by 1g, be scattered in water, obtain the dispersion liquid that mass concentration is 10%, accurately take dispersion liquid 8mg(error 0.2mg), by sample uniform application on quartz colorimetric utensil 3M adhesive tape, claim five Duplicate Samples;
(5), the article colorimetric ware prepared is placed in room temperature under, dry 30min;
(6), by testing sample cuvette be placed in sample arm, another quartz cell posting adhesive tape is placed in reference light paths, measures the ultraviolet light absorption angle value of 280nm ~ 400nm district setting wavelength respectively, then measured value is asked arithmetic mean of instantaneous value ā;
Sequentially determining five parallel sample ā 1 ~ ā 5, ask arithmetic mean of instantaneous value, are exactly the ultraviolet light absorption angle value ā sample of sample, the results are shown in Table 1.
the sun-proof capacity measurement data of polysiloxane composite particles of the chemical sun that the coated OXYBENZONE of table 1 is formed
| Sequence number | Wavelength | Absorbance (ā) |
| 1 | 280.00nm | 0.996A |
| 2 | 290.00nm | 1.001A |
| 3 | 300.00nm | 1.160A |
| 4 | 310.00nm | 1.090A |
| 5 | 320.00nm | 1.100A |
| 6 | 330.00nm | 1.104A |
| 7 | 340.00nm | 0.983A |
| 8 | 350.00nm | 1.086A |
| 9 | 360.00nm | 1.070A |
| 10 | 370.00nm | 1.017A |
| 11 | 380.00nm | 1.104A |
| 12 | 390.00nm | 1.098A |
| 13 | 400.00nm | 1.106A |
(test condition: slit: 2.00 nm wavelength numbers: 13)
Result from table 1 can find out there is good absorbability between wavelength 290nm ~ 400nm, can illustrate that the polysiloxane composite particles of the chemical sun that coated OXYBENZONE is formed has certain anti-sunlight function.
embodiment 2
A polysiloxane composite particles for the chemical sun that coated UVNUL MS-40 is formed, prepare by the following method:
(1) preparation of the nanoemulsions of the chemical sun that UVNUL MS-40 is formed, is comprised
The described nanoemulsions comprising the chemical sun that UVNUL MS-40 is formed is calculated by mass percentage, its raw material composition and content as follows:
Sunscreen 0.1%
Emulsifying agent 0.1%
Oils and fats 0.1%
Help Emulsion 0.1%
Surplus is water;
The chemical sun that described sunscreen is formed for comprising UVNUL MS-40, the product that ISP International Specialty Products company limited produces;
Described emulsifying agent is ten polyglycereol monostearates, and Lonza(dragon is husky) emulsifying agent for cosmetics of Chemical Co., Ltd.;
Described oils and fats is polydimethylsiloxane, Dowcorning(DOW CORNING) Chemical Co., Ltd. produce product;
Described co-emulsifier is the grade product of glycerol, traditional Chinese medicines group;
The above-mentioned nanoemulsions preparation process comprising the chemical sun that UVNUL MS-40 is formed is as follows:
First chemical sun UVNUL MS-40 formed, emulsifying agent, oils and fats and help being uniformly mixed of Emulsion, the chemical sun that UVNUL MS-40 is formed, emulsifying agent, oils and fats and help the mixture being uniformly mixed gained of Emulsion and water to be heated to 60 ~ 80 DEG C respectively; The chemical sun while homogenizing water, UVNUL MS-40 formed, emulsifying agent, oils and fats and help the mixture being uniformly mixed gained of Emulsion to add wherein, homogenizing speed is 10000r/min, homogenizing time 3min, then stir the nanoemulsions being cooled to room temperature and must comprising the chemical sun that UVNUL MS-40 is formed, above-mentioned whipping process controls mixing speed 100r/min;
(2), the preparation of organic silicon monomer hydrolysising product solution
3g trimethylmethoxysilane is placed in 97g water and alcohol mixeding liquid, water: ethanol is 25:75, pH regulator to 4.0 ~ 5.0 to be hydrolyzed reaction with hydrochloric acid solution, hydrolysis time is 2h, temperature 25 DEG C, mixing speed 80r/min, obtains organic silicon monomer hydrolysising product solution after having reacted;
(3) preparation of the polysiloxane composite particles suspension of the chemical sun, formed containing coated UVNUL MS-40
Organic silicon monomer hydrolysising product solution 50g step (2) obtained mixes with the nanoemulsions 50g comprising the chemical sun that UVNUL MS-40 is formed of step (1) gained, then pH is regulated to be 8.5 ~ 9.5 with ammonia, control temperature is 15 DEG C, mixing speed is 150r/min, the suspension containing coated N, N-amyl dimethyl paraaminobenzoic acid chemical sun polysiloxane composite particles is obtained after time 5h;
By the suspension containing the polysiloxane composite particles of the chemical sun that coated UVNUL MS-40 is formed of gained, with water, ethanol circulation cleaning 3 times, and centrifugal, filtration, dry 8h at 150 DEG C, obtain the polysiloxane composite particles of the chemical sun that the nano level coated UVNUL MS-40 of 1.7g is formed, its particle diameter is 0.7 μm.
embodiment 3
A polysiloxane composite particles for the chemical sun that coated benzophenone-5 is formed, prepare by the following method:
(1) preparation of the nanoemulsions of the chemical sun that benzophenone-5 is formed, is comprised
The described nanoemulsions comprising the chemical sun that benzophenone-5 is formed is calculated by mass percentage, its raw material composition and content as follows:
Sunscreen 10%
Emulsifying agent 20%
Oils and fats 10%
Help Emulsion 20%
Surplus is water;
The chemical sun that described sunscreen is formed for benzophenone-5, the product that ISP International Specialty Products company limited produces;
Described emulsifying agent is six polyglycereol monolaurates, and Lonza(dragon is husky) emulsifying agent for cosmetics of Chemical Co., Ltd.;
Described oils and fats is cyclic methyl siloxane, Dowcorning(DOW CORNING) Chemical Co., Ltd. produce product;
Described co-emulsifier is the grade product of isopropyl alcohol, traditional Chinese medicines group;
The above-mentioned nanoemulsions preparation process comprising the chemical sun that benzophenone-5 is formed is as follows:
First the chemical sun formed by benzophenone-5, emulsifying agent, oils and fats and help being uniformly mixed of Emulsion, by sunscreen, emulsifying agent, oils and fats with help the mixture being uniformly mixed gained of Emulsion and water to be heated to 80 ~ 90 DEG C respectively; The chemical sun while homogenizing water, benzophenone-5 formed, emulsifying agent, oils and fats and help the mixture being uniformly mixed gained of Emulsion to be added to the water, continue homogenizing, homogenizing process control rate is 50000r/min, time is 2min, stir the nanoemulsions being cooled to room temperature and must comprising the chemical sun that benzophenone-5 is formed after homogenizing, above-mentioned whipping process controls mixing speed 150r/min;
(2), the preparation of organic silicon monomer hydrolysising product solution
15g trimethylmethoxysilane is placed in 85g water and alcohol mixeding liquid, water: ethanol is 50:50, pH regulator to 3.0 ~ 4.0 to be hydrolyzed reaction with hydrochloric acid solution, hydrolysis time is 2.5h, temperature 20 DEG C, mixing speed 70r/min, obtains organic silicon monomer hydrolysising product solution after having reacted;
(3) preparation of the suspension of the nano polysilicon oxygen alkane compound particle of the chemical sun, formed containing coated benzophenone-5
Organic silicon monomer hydrolysising product solution 90g step (2) obtained mixes with the nanoemulsions 10g comprising the chemical sun that benzophenone-5 is formed of step (1) gained, then pH is regulated to be 7.5 ~ 8.5 with ammonia, control temperature is 20 DEG C, mixing speed is 100r/min, obtains the suspension of the chemical sun polysiloxane composite particles formed containing coated benzophenone-5 after time 5h;
By the suspension containing the polysiloxane composite particles of the chemical sun that coated benzophenone-5 is formed of gained, with water, ethanol circulation cleaning 3 times, and centrifugal, filtration, dry 5h at 200 DEG C, obtain the polysiloxane composite particles of the chemical sun that the nano level coated benzophenone-5 of 19.5g is formed, its particle diameter is 0.9 μm.
embodiment 4
A polysiloxane composite particles for the chemical sun that coated OXYBENZONE is formed, prepare by the following method:
(1) preparation of the nanoemulsions of the chemical sun that OXYBENZONE is formed, is comprised
With embodiment 1;
(2), the preparation of organic silicon monomer hydrolysising product solution
8g dimethyldiethoxysilane is placed in 92g water and alcohol mixeding liquid, water: ethanol is 1:99, pH regulator to 3.5 ~ 4.5 to be hydrolyzed reaction with hydrochloric acid solution, hydrolysis time is 4.5h, temperature 30 DEG C, mixing speed 90r/min, obtains organic silicon monomer hydrolysising product solution after having reacted;
(3) preparation of the suspension of the polysiloxane composite particles of the chemical sun, formed containing coated OXYBENZONE
The nanoemulsions 30g that organic silicon monomer hydrolysising product solution 70g step (2) obtained and step (1) are formed mixes, then pH is regulated to be 7.5 ~ 8.5 with ammonia, control temperature is 25 DEG C, mixing speed is 100 r/min, obtains the suspension of the polysiloxane composite particles of the chemical sun formed containing coated OXYBENZONE after time 5h;
By the suspension containing the polysiloxane composite particles of the chemical sun that coated OXYBENZONE is formed of gained, with water, ethanol circulation cleaning 3 times, and centrifugal, filtration, dry 10h at 100 DEG C, obtain the polysiloxane composite particles of the chemical sun that the nano level coated OXYBENZONE of 11.6g is formed, its particle diameter is 0.8 μm.
embodiment 5
A polysiloxane composite particles for the chemical sun that coated UVNUL MS-40 is formed, prepare by the following method:
(1) preparation of the nanoemulsions of the chemical sun that UVNUL MS-40 is formed, is comprised
With embodiment 2;
(2), the preparation of organic silicon monomer hydrolysising product solution
3g MTES is placed in 97g water and alcohol mixeding liquid, water: ethanol is 25:75, pH regulator to 3.0 ~ 4.0 to be hydrolyzed reaction with hydrochloric acid solution, hydrolysis time is 4.0h, temperature 25 DEG C, mixing speed 60r/min, obtains organic silicon monomer hydrolysising product solution after having reacted;
(3) preparation of the suspension of the nano polysilicon oxygen alkane compound particle of the chemical sun, formed containing coated UVNUL MS-40
The nanoemulsions 50g that organic silicon monomer hydrolysising product solution 50g step (2) obtained and step (1) are formed mixes, then pH is regulated to be 8.5 ~ 9.5 with ammonia, control temperature is 15 DEG C, mixing speed is 150r/min, obtains the suspension of the polysiloxane composite particles of the chemical sun formed containing coated UVNUL MS-40 after time 5h;
By the suspension containing the polysiloxane composite particles of the chemical sun that coated UVNUL MS-40 is formed of gained, with water, ethanol circulation cleaning 3 times, and centrifugal, filtration, dry 8h at 150 DEG C, obtain the polysiloxane composite particles of the chemical sun that the nano level coated UVNUL MS-40 of 1.7g is formed, its particle diameter is 0.7 μm.
embodiment 6
A nano polysilicon oxygen alkane compound particle for the chemical sun that coated benzophenone-5 is formed, prepare by the following method:
(1) preparation of the nanoemulsions of the chemical sun that benzophenone-5 is formed, is comprised
With embodiment 3;
(2), the preparation of organic silicon monomer hydrolysising product solution
15g tetraethoxysilane is placed in 85g water and alcohol mixeding liquid, water: ethanol is 50:50, pH regulator to 3.0 ~ 4.0 to be hydrolyzed reaction with hydrochloric acid solution, hydrolysis time is 3.5h, temperature 25 DEG C, mixing speed 100r/min, obtains organic silicon monomer hydrolysising product solution after having reacted;
(3) preparation of the suspension of the polysiloxane composite particles of the chemical sun, formed containing coated benzophenone-5
Hydrolysising product solution 90g step (2) obtained mixes with the nanoemulsions 10g comprising the chemical sun that benzophenone-5 is formed of step (1) gained, then pH is regulated to be 7.5 ~ 8.5 with ammonia, control temperature is 20 DEG C, mixing speed is the suspension obtaining the polysiloxane composite particles of the chemical sun formed containing benzophenone-5 after 100r/min, 5h;
By the suspension containing the polysiloxane composite particles of the chemical sun that coated benzophenone-5 is formed of gained, with water, ethanol circulation cleaning 3 times, and centrifugal, filtration, dry 5h at 200 DEG C, obtain the polysiloxane composite particles of the chemical sun that the nano level coated benzophenone-5 of 19.5g is formed, its particle diameter is 0.9 μm.
Foregoing be only the present invention conceive under basic explanation, and according to any equivalent transformation that technical scheme of the present invention is done, all should protection scope of the present invention be belonged to.
Claims (6)
1. the polysiloxane composite particles of chemical sun that formed of coated Benzophenones, is characterized in that preparing by the following method:
(1) preparation of the nanoemulsions of the chemical sun that Benzophenones is formed, is comprised
The described nanoemulsions comprising the chemical sun that Benzophenones is formed is calculated by mass percentage, its raw material composition and content as follows:
Sunscreen 0.1 ~ 10%
Emulsifying agent 0.1 ~ 20%
Oils and fats 0.1 ~ 10%
Help Emulsion 0.1 ~ 20%
Surplus is water;
The chemical sun that described sunscreen is formed for Benzophenones;
The chemical sun that described Benzophenones is formed is benzophenone-1, one or more mixture formed in benzophenone-2, OXYBENZONE, UVNUL MS-40, benzophenone-5, benzophenone-6 and Benzophenone-9;
The above-mentioned nanoemulsions preparation process comprising the chemical sun that Benzophenones is formed is as follows:
First chemical sun Benzophenones formed, emulsifying agent, oils and fats and help being uniformly mixed of Emulsion, then while homogenizing water, the chemical sun that Benzophenones is formed, emulsifying agent, oils and fats and help the mixture being uniformly mixed gained of Emulsion to be added to the water, continue homogenizing, it is 10000 ~ 50000r/min that homogenizing process controls homogenizing speed, time is 0.1 ~ 30min, after homogenizing, stirring is cooled to room temperature and namely obtains the nanoemulsions comprising the chemical sun that Benzophenones is formed, it is 10 ~ 1000r/min that above-mentioned whipping process controls mixing speed,
Described emulsifying agent is anion surfactant or non-ionic surface active agent;
Wherein said anion surfactant is fatty alcohol sulfate salt, and its molecular formula is C
nh
2n+1sO
4m, wherein n is 11 ~ 17, M is Na, K or NH
3;
Described non-ionic surface active agent is four polyglycereol monostearates, four polyglycereol five stearates, four polyglycerol monooleate, four polyglycereol five oleates, four polyglycereol monolaurates, six polyglycereol monostearates, six polyglycereol five stearates, six polyglycerol monooleate, six polyglycereol five oleates, six polyglycereol monolaurates, eight polyglycereol monostearates, eight polyglycereol eight stearates, eight polyglycerol monooleate, eight polyglycereol monolaurates, ten polyglycereol monostearates, ten polyglycereol five stearates, ten polyglycerol monooleate or ten polyglycereol monolaurates,
Described oils and fats be mineral grease, natural origin Vegetable oil lipoprotein, natural origin animal oil and synthetic ester oil one or more rich mixture,
Described mineral grease is white oil, ceresine or microwax;
Described natural origin Vegetable oil lipoprotein is olive oil, palm-kernel oil, American Avocado Tree oil, soybean oil, Testa oryzae oil, Apricot kernel oil, Oleum helianthi, Camellia oil, cocoa butter, mother-in-law sieve's fat, mowrah fat, Adeps Bovis seu Bubali resin, Brazil wax or aromatic wax;
Described natural origin animal oil is Adeps Serpentis, horse fat or spermaceti;
Described synthetic ester oil is methyl polysiloxane, methyl phenyl silicone, Methyl Hydrogen Polysiloxane Fluid, polyether modified silicon oil, long chain alkyl modified silicon oil, cyclic polysiloxanes, amino-modified silicone oil, Carboxyl Modified Polydimethylsiloxane, methyl polysiloxane emulsion, Organosilicon wax or silicones;
Described co-emulsifier is monohydric alcohol or polyhydric alcohol, and wherein the molecular formula of monohydric alcohol is C
nh
2n+1oH, wherein n is between 1 ~ 12; Polyhydric alcohol is ethylene glycol, 1,2-PD, 1,3-PD, 1, one or more mixed alcohols formed in 3 butanediols, propylene carbonate and glycerol;
(2), the preparation of organic silicon monomer hydrolysising product solution
Organosilicon is added in the mixture of water and/or organic solvent, then under acid or alkali effect, control pH be 1 ~ 6 or pH 7.5 ~ 11.5 to be hydrolyzed reaction, hydrolysis time was at 0.1 ~ 10 hour, temperature 1 ~ 100 DEG C, mixing speed 10 ~ 1000r/min, obtains organic silicon monomer hydrolysising product solution after having reacted;
Described organosilyl addition calculates i.e. organosilicon in mass ratio: the mixture of water and/or organic solvent is 1 ~ 50:100;
Described organosilicon is organosiloxane, and its structural formula is R
1nSiX
(4-n);
Wherein R
1that representative is selected from replacement or the unsubstituted univalent perssad having a C atom to be connected directly between alkyl on Si atom or alkenylphenyl, n is the integer of 0 ~ 3, X is hydrolysising group, is hydroxyl, hydrogen, alkoxyl, halogen group, carboxyl, amino or siloxy;
As n > 1, each R1 group can be identical or different;
And as (4-n) > 1, each X group can be identical or different;
Said organic solvent is methanol, ethanol, ethylene glycol, propanol, isopropyl alcohol, butanols, isobutanol, propylene carbonate, glycerol, Methanamide, N, the mixture of one or more compositions in N-dimethyl acetylamide, DMF, acetone, oxolane, dimethylsulfone, ethyl acetate, pyridine and acetonitrile;
(3) preparation of the suspension of the polysiloxane composite particles of the chemical sun, formed containing coated Benzophenones
The organic silicon monomer hydrating solution obtain step (2) and the nanoemulsions comprising the chemical sun that Benzophenones is formed of step (1) gained calculate in mass ratio, the i.e. nanoemulsions of chemical sun that formed of Benzophenones: organic silicon monomer hydrolysising product solution is that 0.1:99.9 ~ 50:50 mixes, then the suspension of the polysiloxane composite particles of the chemical sun formed containing coated Benzophenones is obtained after carrying out polycondensation reaction under regulating with alkaline matter the condition that pH is 7.5 ~ 13.5, it is 0 DEG C ~ 100 DEG C that polycondensation process controls reaction temperature, rotating speed is 10 ~ 1000r/min, time is 0.1 ~ 24h,
The suspension water, the ethanol circulation cleaning that contain the polysiloxane composite particles of the chemical sun that coated Benzophenones is formed that to obtain after polycondensation reaction completes, and centrifugal, filtration, by dry at 100 ~ 200 DEG C for the filter cake obtained, the solids finally obtained are the polysiloxane composite particles of the chemical sun that coated Benzophenones is formed.
2. the polysiloxane composite particles of chemical sun that formed of a kind of coated Benzophenones as claimed in claim 1, is characterized in that the organosilan described in step in preparation process (2) is trimethylmethoxysilane, trimethylethoxysilane, trimethyl silanol, tri-phenyl chloride, trim,ethylchlorosilane, dimethyldichlorosilane, diethyl dichlorosilane, Methylethyl dichlorosilane, dimethyl chloride methoxy silane, diphenyl dichlorosilane, dimethoxydiphenylsilane, diphenyl diethoxy silane, dimethyldimethoxysil,ne, dimethyldiethoxysilane, aminomethyl phenyl dimethoxysilane, methyltrimethylsilane, MTES, phenyltrimethoxysila,e, phenyl triethoxysilane, hexyl trimethoxy silane, octyltri-ethoxysilane, decyl trimethoxy silane, vinyltrimethoxy silane, VTES, methyl allyl acyloxypropyl trimethoxysilane, methyl trichlorosilane, phenyl trichlorosilane, tetramethoxy-silicane, tetraethoxysilane, one or more organosilane mixtures formed in four butoxy silanes and tetrachloro silicane.
3. the polysiloxane composite particles of chemical sun that formed of a kind of coated Benzophenones as claimed in claim 1, is characterized in that:
Acid described in step (2) is citric acid, one or more mixture formed in acetic acid, oxalic acid, tartaric acid, hydrochloric acid, phosphoric acid, carbonic acid and sulfurous acid;
Alkali described in step (2) is the mixture of one or more compositions in sodium carbonate, sodium bicarbonate, sodium hydroxide, potassium hydroxide, ammonia, methylamine, dimethylamine, ethamine, diethylamine and triethylamine.
4. the polysiloxane composite particles of chemical sun that formed of a kind of coated Benzophenones as claimed in claim 1, is characterized in that the alkaline matter of step (3) is sodium carbonate, sodium bicarbonate, sodium hydroxide, potassium hydroxide, ammonia, methylamine, dimethylamine, ethamine, diethylamine or triethylamine.
5. a kind of coated Benzophenones as described in as arbitrary in Claims 1 to 4 the polysiloxane composite particles of chemical sun that formed, it is characterized in that:
The hydrolysis preferred control time described in step (2) is 2 ~ 4.5h, and temperature is 15 ~ 30 DEG C, and mixing speed is 60 ~ 100r/min;
The preferred control temperature of polycondensation process described in step (3) is 5 ~ 25 DEG C, and rotating speed is 100 ~ 150r/min, and the time is 5h.
6. a kind of coated Benzophenones as described in as arbitrary in Claims 1 to 4 the polysiloxane composite particles of chemical sun that formed, it is characterized in that the particle diameter of the polysiloxane composite particles of the chemical sun that described coated Benzophenones is formed is 100nm ~ 300nm.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110439641.3A CN102488625B (en) | 2011-12-26 | 2011-12-26 | Benzophenone-type chemical sun-screening agent-coated polysiloxane composite particle and preparation method thereof |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1506367A (en) * | 2002-12-06 | 2004-06-23 | 河南省科学院同位素研究所 | Organosilicon modified cinnamate as reactive ultraviolet ray absorbent and its prepn and application |
| CN101589997A (en) * | 2009-06-25 | 2009-12-02 | 上海应用技术学院 | A kind of UVB ultra light sun block lotion and preparation method thereof |
| CN101849891A (en) * | 2008-12-04 | 2010-10-06 | 国际香料和香精公司 | The microcapsule that contains active component |
-
2011
- 2011-12-26 CN CN201110439641.3A patent/CN102488625B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1506367A (en) * | 2002-12-06 | 2004-06-23 | 河南省科学院同位素研究所 | Organosilicon modified cinnamate as reactive ultraviolet ray absorbent and its prepn and application |
| CN101849891A (en) * | 2008-12-04 | 2010-10-06 | 国际香料和香精公司 | The microcapsule that contains active component |
| CN101589997A (en) * | 2009-06-25 | 2009-12-02 | 上海应用技术学院 | A kind of UVB ultra light sun block lotion and preparation method thereof |
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