CN100560052C - Compound particle and manufacture method thereof - Google Patents
Compound particle and manufacture method thereof Download PDFInfo
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- CN100560052C CN100560052C CNB2005101057309A CN200510105730A CN100560052C CN 100560052 C CN100560052 C CN 100560052C CN B2005101057309 A CNB2005101057309 A CN B2005101057309A CN 200510105730 A CN200510105730 A CN 200510105730A CN 100560052 C CN100560052 C CN 100560052C
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Abstract
The present invention has provided a kind of compound particle and manufacture method thereof, and the cosmetic that contains this compound particle.Compound grain provided by the invention and manufacture method thereof, and the cosmetic that contains this compound particle, be to contain polyolefin resin and the zinc oxide of degree of crystallinity below 80%, the compound particle that obtains with fusion dispersion method or molten atomizing cooling method, or contain the particle of degree of crystallinity 80% following polyolefin resin and zinc oxide, wherein, 25 ℃ 0.5mol/L hydrochloric acid solution (solution composition, water and ethanol are the equal-volume ratio) middle dipping is after 1 hour, and the zinc oxide survival rate in the particle is more than 50 weight %.
Description
Technical field
The present invention relates to contain the compound particle and the manufacture method thereof of polyolefin resin and zinc oxide and the cosmetic that contains this compound particle.
Background technology
In recent years, because the ozone layer part is destroyed, the ultraviolet amount on arrival point surface increases, and the serious hope that efficiently prevents the cosmetic that Exposure to Sunlight is burnt is also grown with each passing day.At present, prevent burn UV absorbent in the cosmetic of Exposure to Sunlight as this type of, use organic compound such as benzophenone, benzoic acids, methoxy cinnamic acid, but these organic compound exist can not absorb the ultraviolet in wide wavelength range territory, skin is had problem such as zest, so require safer ultraviolet light screener.
Arrive in the ultraviolet on the face of land, except short wavelength ultraviolet (the B zone: 280～320nm) of inflammation (so-called Exposure to Sunlight is burnt) such as causing herpes, erythematous eruption is arranged, also has more long wavelength's ultraviolet (a-quadrant: 320～400nm), clearly this stack result causes skin aging and concurrent cancer easily, so in recent years, particularly pay close attention to the ultraviolet that how to shield the a-quadrant.
Zinc oxide has sharp-pointed absworption peak originally near 380nm, so the ultraviolet shielding effect to the a-quadrant is very high, further developed ultra-fine particles of zinc oxide afterwards, this ultra-fine particles of zinc oxide, can not only shield by the B zone ultraviolet in the very wide wavelength domain in a-quadrant, and the ultramicron Titanium Dioxide Rutile Top grade has 2.7 refractive index, and the refractive index of ultra-fine particles of zinc oxide is less than 2.0, the transparency is good, so extensively gazed at as ultraviolet light screener.
On the other hand, zinc oxide has the character that is slightly soluble in water originally, and the physiological action that zinc ion produces is separated out in its dissolving, uses as astringent in cosmetic field since ancient times.Moreover, have the chemical reactivity that generates metallic soap with fatty acid response, can absorb the excretory sebum of skin, have good maintenance dressing effect, also can utilize its deodorizing effect to absorb the body odor composition.
These physiologically actives and chemical reactivity have the tendency of further reinforcement by the ultramicron zinc oxide, from now on, when further requiring relative skin histology stable, preferably can suppress the activity of particle surface.
In addition, in the matching design of cosmetic, above-mentioned zinc oxide can bring various unsafty problems to the dissolubility and the chemical reactivity of water.That is, cosmetic most important material composition is the main constituent water of human body, but contains the cosmetic of ultra-fine particles of zinc oxide, because the dissolving zinc ion of separating out reacts with other compositions, so can not improve the ratio of water, causes the degree of freedom of writing out a prescription narrow.For example, the anti-Exposure to Sunlight that contained ultra-fine particles of zinc oxide is in the past burnt in the cosmetic, is difficult to make the ratio of water to reach more than 50%, and most emulsifying goods only are defined as water in oil (W/O).Such emulsifying goods are oil matrix, are difficult to obtain salubrious usability.
Moreover, when ultra-fine particles of zinc oxide uses in cosmetic, because other gradation compositions of ultra-fine particles of zinc oxide and cosmetics, as various oil preparationes, spice, colorant, organic uv absorbers, water soluble polymer etc. react, can cause that cosmetic viscosity increases or reduces, produces problems such as foreign odor, variable color, cause the degree of freedom of filling a prescription narrow.
Therefore, a kind of technology is disclosed among the JP-A3-183620, promptly, the oxide of aluminium coating, silicon, zirconium or stannum or hydroxide on the micropartical zinc oxide surface, the catalytic activity of zinc oxide is reduced, organic class carrier is rotten in the inhibition cosmetic, reduces the dyanainic friction coefficient of micropartical zinc oxide, can prevent that slickness and sense of touch from worsening.
Disclose a kind of technology among the JP-A11-302015, that is,, be suppressed at the dissolubility in the pure water on the zinc oxide particle surface by the high density cover layer that is formed by Si oxide is set.
Disclose a kind of technology among the JP-A8-53568, that is,,, suppressed of the effect of other compositions carrier with having disperseed the monomer phase particlized of zinc oxide by outstanding turbid polymerization or emulsion polymerization method.As the monomer that common outstanding turbid or emulsion polymerization body apoplexy due to endogenous wind uses, can enumerate styrene, methyl methacrylate, acrylonitrile, vinyl acetate etc., but the polymer resistance to chemical reagents that obtains is all very poor.
The methyl methacrylate that uses among the embodiment of JP-A8-53568 has ester bond, and resistance to chemical reagents is insufficient.Relatively usually, ethanol and the oil preparation that cooperates in the cosmetic presents dilatancy, in fact do not reach the reaction of other compositions such as abundant inhibited oxidation zinc and carrier.
On the other hand, when using with the micropartical original state usually, be easy to form agglomerate.For this reason, be dispersed in micropartical in the monomer after, polymerization single polymerization monomer is also fixing, perhaps micropartical behind the dispersion milling, is made resin solidification in molten resin, forms fixture.
Micropartical is fixed on method in the cured resin,, can under molten condition, in gas phase, sprays, perhaps treat to pulverize behind the resin solidification in order to make the resin formation small particle diameter.
Therefore, a kind of technology of using the board-like nozzle of rotational circle molten resin to be carried out spray cooling is disclosed in JP-A6-167835.
Summary of the invention
The invention provides a kind of compound particle and contain the cosmetic of this compound particle, be to contain degree of crystallinity at polyolefin resin below 80% and zinc oxide, the compound particle that obtains with fusion dispersion method or molten atomizing cooling method, or contain the particle of degree of crystallinity at polyolefin resin below 80% and zinc oxide, it is characterized in that, dipping is after 1 hour in the hydrochloric acid solution (water of solution composition and ethanol are the equal-volume ratio) of 25 ℃ of following 0.5mo/L, and the zinc oxide survival rate is more than 50 weight % in the particle.
In addition, the invention provides a kind of manufacture method of above-mentioned compound particle, it is characterized in that, after polyolefin resin and zinc oxide mixing, under the temperature more than the polyolefin resin softening temperature (or fusing point), this mixture is sprayed to cooling curing in the cryogen, and its feature also is, uses 3 fluids to spray with top nozzle.
Description of drawings
Fig. 1 is the sketch map of an example of 4 fluid linear type nozzles.
Fig. 2 is the sketch map of an example of 3 fluid pencil-type nozzles, (a) is front elevation, (b) is plane graph.
Symbol description
The stream of the melting mixing thing of 1 resin and zinc oxide; The stream of 2 spray gas; 3 spray particles; 4 nozzle edges; 5 conflict focuses
The specific embodiment
Use that the surface is provided with tectal zinc oxide fine particles among the JP-A3-183620, very insufficient to the inhibition of photocatalytic activity, the water-soluble and the chemical reactivity that especially almost can not controlled oxidation zinc have originally.
Find also that in the embodiment of JP-A11-302015 the goods medium viscosity of preserving 7 days under the room temperature has reduction slightly.
The diameter of the resin particle that use JP-A6-167835 method obtains is 30～200 μ m, has the boundary of small particle diameterization.
The invention provides a kind of compound particle and manufacture method thereof, and the cosmetic that contains this compound particle, can solve in the variety of issue of above-mentioned zinc oxide, as burn problem in the ultra-fine particles of zinc oxide that cosmetic uses of anti-Exposure to Sunlight, it is inhibited oxidation zinc surface activity highly, has high transparent and ultraviolet-shielding type simultaneously.
Compound particle of the present invention, the remarkable dissolubility of inhibited oxidation zinc in pure water and aqueous hydrochloric acid solution, and surface activity that can height inhibited oxidation zinc, have the very high transparency and ultraviolet-shielding type simultaneously, extremely suit to use in cosmetic in ultraviolet screener.
Manufacture method of the present invention, particularly by using the nozzle more than 3 fluids to spray, the compound particle that obtains is that ultra-fine particles of zinc oxide is dispersed in the resin, below the volume average particle size 30 μ m of compound particle, and the following compound particle of particle ratio more than 15 volume % of particle diameter 5 μ m.
[polyolefin resin]
From the surface activity of inhibited oxidation zinc, reduce the dissolubility aspect of zinc oxide and consider that the polyolefin resin that uses among the present invention uses the polyolefin resin of degree of crystallinity below 80%, preferably uses degree of crystallinity at the polyalkenes resin below 70%.At this moment, different types of polyolefin resin can be mixed and use, the degree of crystallinity of polyolefin resin mixture is getting final product below 80%.
Degree of crystallinity can be utilized X-ray diffraction method, obtains under following condition determination.
(condition determination of X-ray diffraction method)
Device name: motor of science (strain) system, R1NT2500
The multiplet partition method
Line source: CuKa
Tube current: 120mA
Tube voltage: 40KV
Scanning speed: 10 °/min
As polyolefin resin, can enumerate alkenes copolymers such as the independent polymer of alkene, propylene and ethylene random copolymer such as polyethylene, polypropylene, poly-1-butylene, polymethylpentene, poly-methyl butene, polybutadiene etc.Also can use polytetrafluoroethylene (PTFE) etc. to have the polyolefin of fluorine atom.In these polyolefin resins, preferably polyethylene.From zinc oxide favorable dispersibility aspect is considered, the most effective as the acid polyethylene modifier.
The polyolefin resin that uses among the present invention, the material that preferred molten viscosity is low.Consider that from the aspect that compound particle is easy to manufacture the fusing point of polyolefin resin or softening temperature are preferably more than 80 ℃, more preferably more than 100 ℃, though the unqualified upper limit is considered from the easiness of making, preferably below 200 ℃.The fusing point of polyolefin resin can utilize JLSK0064:1992 to measure.
Consider that from the melt viscosity of resin and intensity aspect the molecular weight of polyolefin resin is preferred 500～20000, more preferably 1000～10000, the molecular weight of polyolefin resin can utilize viscosimetry to try to achieve.
[zinc oxide]
In order to obtain ultraviolet-shielding type, zinc oxide of the present invention is the following zinc oxide of 0.1 μ m with particle diameter preferably, in order to improve the mixing property with polyolefin resin, the zinc oxide that hydrophobization is handled is carried out on the preferred surface of using in advance, surface treatment method as zinc oxide, can enumerate and utilize surface treatment that organic silicone carries out etc., but be not limited to this.
[compound particle]
Compound particle of the present invention, be with zinc oxide and degree of crystallinity at the polyolefin resin below 80% as main constituent, so in the scope of not damaging effect of the present invention, also can contain other compositions, for example, inorganic and pigment, surfactant, silicone compounds or antioxidants etc. such as organic pigment, organic dyestuff.
From considering to the adaptability of following manufacture method with to ultraviolet shield effectiveness aspect, the ratio of polyolefin resin and zinc oxide in the compound particle, polyolefin resin/zinc oxide (weight ratio) is preferably 99/1～30/70, more preferably 95/5～50/50, be preferably 80/20～60/40 especially.
From suppressing harsh feeling and preventing tanned consideration, the volume average particle size of compound particle of the present invention, preferred 0.5～30 μ m, more preferably 2～10 μ m.
Volume average particle size is to utilize Coulter counter (device name: Beckman Coulter society system, the value of LS-230) measuring in ethanol.
[manufacture method of compound particle]
As the manufacture method of compound particle of the present invention, preferably use fusion dispersion method or molten atomizing cooling method, more preferably use the molten atomizing cooling method.As additive method, can enumerate spray drying method, hybrid method in principle, uses these methods to be easy to produce slight crack and hole on the compound particle surface, is difficult to make zinc oxide and extraneous formation shielding.
So-called fusion dispersion method, be with dispersate and zinc oxide such as polyolefin resins, with the disperse medium immiscible, in the temperature environment more than dispersate fusing point (or softening point), utilize the effect of mechanical shear stress and dispersant with it, after being distributed to desired particle diameter, be cooled to the following temperature of fusing point (or softening point) of dispersate again, the method that obtains with solids, for example, polyethylene can be enumerated as dispersate, water or glycerol can be enumerated as disperse medium.These operations can under high pressure be carried out.
The molten atomizing cooling method, be with after polyolefin resin and the zinc oxide mixing, under the temperature more than the softening temperature (or fusing point) of polyolefin resin, this mixture is sprayed in the cold medium, the method of cooling curing, make the compound particle that obtains in this way, be not easy to produce in its surface slight crack and hole, and zinc oxide and extraneous formation are shielded.
In the manufacture method of the present invention, at first polyolefin resin and zinc oxide are carried out premixing.Consider from obtaining good ultraviolet shielding effect aspect, this moment polyolefin resin and zinc oxide the cooperation ratio, the weight ratio of polyolefin resin/zinc oxide is preferably 99/1～30/70, more preferably 95/5～50/50, be preferably 80/20～60/40 especially.For obtaining the excellent ultraviolet-shielding type and the transparency, preferably carry out mixingly, be near under the state of disposable particle, zinc oxide is dispersed in the polyolefin resin.As the equipment that uses in mixing, can enumerate jet mixer, Planetary, kibbler roll (roll mill), Needer, extruder etc.
Then, said mixture is heated to more than the softening humidity (or fusing point) of polyolefin resin, form the mixing thing of heat fusing, use disc type aerosol apparatus (disc atomizer), use 1 fluid or more than 2 fluids, more than preferred 2 fluids, the more preferably above multithread body nozzle of 3 fluids, be sprayed in preferred 5～50 ℃ cold medium, cooling curing reclaims compound particle.Preferably be sprayed in the cold medium with Compressed Gas.As cold medium, be preferably gas phase especially.Compressed Gas as fluid uses preferably uses 9.8 * 10
4More than the Pa, more preferably use 9.8 * 10
4～29.4 * 10
4The compressed air of Pa or compressed nitrogen.This gas can use and be heated to the above gas of vapo(u)rizing temperature, stops up to prevent nozzle segment from being cooled off, owing to can make particle continuously, therefore preferred.
Consider that from the corpusculed performance of spray particle and the simple and easy degree of structure the multithread body nozzle as more than 3 fluids preferably uses pencil-type nozzle, linear type nozzle, especially preferably uses 3 fluidic pencil-type nozzles, 4 fluidic linear type nozzles etc.Pencil-type nozzle and linear type nozzle compare, owing to utilize contracted flow, the fluid velocity of conflict point and crushing force are very big, therefore are more preferably.What Fig. 1 represented is an example of 4 fluidic linear type nozzles, and what Fig. 2 represented is an example of 3 fluidic pencil-type nozzles.(a) is that front elevation, (b) are plane graph among Fig. 2.Among Fig. 1 and Fig. 2, the 1st, the stream of resin and zinc oxide melting mixing thing, the 2nd, the stream of spray gas, the 3rd, spray particle, the 4th, nozzle edge, the 5th, conflict focus.
As 3 fluidic pencil-type nozzles, 4 fluidic linear type nozzles preferably use the rugged motor of rattan (strain) system, the 3 fluid pencil-type nozzles of Micro Mist Dryer MDL-050C, 4 fluid linear type nozzles.
Consider that from obtaining atomic aspect when with nozzle the melting mixing thing being sprayed, the Capacity Ratio of spray gas/mixing thing is preferably more than 1000/1, more preferably more than 5000/1.Though do not have the upper limit of Capacity Ratio, consider that economy is preferably below 100000/1.
Consider to obtain good sprayability, vapo(u)rizing temperature, the mixture viscosity of preferred polyolefm resinoid and zinc oxide reaches below the 800mPas, more preferably below the 300mPas, the following temperature of preferred especially 100mPas though there is not lower limit, preferably reaches the above temperature of viscosity 10mPas.
The present invention can handle above-mentioned compound particle with the anionic surfactant, below elaborate.
[utilizing the anionic surfactant to handle]
Among the present invention, handle preceding particle with the above-mentioned processing of anionic surfactant treatment.Cover the zinc oxide particle that exposes on the compound particle surface by this processing with anion surfactant, or be present in compound particle near surface, the easy zinc oxide particle that dissolves in the environment of separating out, can give the cosmetic that has cooperated this compound particle very high stability.
As the anionic surfactant who uses among the present invention, the preferred material that forms water-insoluble complex with zinc ion that uses.As the simple and easy method of confirming to form water-insoluble complex, can enumerate following method.
The anionic surfactant is modulated into the aqueous solution with light transmission about 0.1～1 weight %.In this aqueous solution of 30mL, mix about 1% solder(ing)acid.At this moment, anionic surfactant's aqueous solution forms the nebulousurine shape, causes the transparency to reduce, and this just means that zinc ion and anionic surfactant have formed the water-insoluble complex.
Specifically; as the anionic surfactant who shows this rerum natura; can enumerate soap, alkylbenzenesulfonate, alkylsulfonate, dialkyl sulfosuccinic salt; N-methyl-N-alkyl taurine, alkylphosphonic, polyoxyethylene alkyl ether phosphate, fluoroalkyl phenylate carbonate, fluoroalkyl phenylate phosphonate etc., can use wherein more than a kind or 2 kinds.As with the salifiable cation of these surfactant shapes, can enumerate alkali metal ion, alkaline-earth metal ion, ammonium ion, alkanol ammonium ion etc.In these cationes, preferred as alkali ion, more preferably sodium ion and potassium ion.
Among these anionic surfactants, preferably the carbon number of alkyl is that the carbon number of 10～20 alkylphosphonic, alkyl is N-methyl-N-alkyl taurine of 10～20.
The processing that particle is undertaken by the anionic surfactant before handling can suitable method make the particle before handling contact with the anionic surfactant.Specifically be that the particle before handling is dispersed in the anionic property agent solution, thereafter, as required, can decompose compound particle and anionic surfactant's solution.As anionic surfactant's solution preferred aqueous solutions, also there is the affinity that can improve particle surface and treatment fluid by alcohol such as an amount of mixed ethanols, can carry out the situation of more effective processing.The blending ratio of water and organic solvent is counted water with weight ratio: organic solvent=100: 0～20: 80.
Handle used anionic surfactant's amount, get 0.1～2 mole with respect to the zinc oxide in the particle before handling and doubly suit.Anionic surfactant's concentration can suitably be regulated in the treatment fluid, be preferably 0.01～6 weight %, 0.1～2 weight % more preferably, consider from the aspect that the more selective zinc oxide that does not make near the part particle surface melts, processing time, preferably carry out in the short time, preferred 1 minute～10 hours, more preferably 3 minutes～5 hours.For particle surface is contacted with the anionic surfactant,, can effectively eliminate interparticle cohesion by using dispersion machines such as homogenizer and quick runner dispersion machine.Treatment temperature, if particle fusion or below the condensation temperature just can, be not particularly limited.
Utilize anionic surfactant's processing, the zinc oxide ratio in the compound particle does not have too big variation, but the ratio of zinc oxide can be measured by the calcination recrement of compound particle before and after handling.As required, can utilize the additive methods such as ICP luminesceence analysis of filtrate.
The zinc oxide containing ratio of handling in the compound particle of back is preferably 1～70 weight %, and more preferably 5～50 weight % are preferably 10～40 weight % especially.
The present invention also can handle above-mentioned compound particle with acid and/or alkali, below is elaborated.
[processing of acid and/or alkali]
Among the present invention, with at least one of from bronsted lowry acids and bases bronsted lowry, selecting to above-mentioned processing before particle handle, utilize this processing can at first remove the zinc oxide particle that exposes on the compound particle surface, or be present in the compound particle near surface and be easy to dissolve the zinc oxide particle of separating out in the environment, can give the cosmetic that has cooperated this compound particle high stability.
As the acid of using among the present invention, can use mineral acid and organic acid, as mineral acid, can enumerate sulphuric acid, hydrochloric acid, nitric acid, phosphoric acid etc.As organic acid, can enumerate divalent organic acid such as 1 valency organic acid such as acetic acid, glycol acid, propanoic acid, lactic acid, gluconic acid, fumaric acid, succinic acid, malic acid, Tartaric acid, citric acid, trimellitic acid 3 valency organic acid such as (1,2,4 one benzene tricarbonic acids) etc.In the organic acid, the sour permeability height that molecular weight is little has the tendency of dissolving compound particle interior oxidation zinc.Therefore, preferably use molecular weight, particularly at 100～1000 organic acid more than 100.
As the alkali that uses among the present invention, can enumerate sodium hydroxide, potassium hydroxide, ammonia, sodium bicarbonate, sodium carbonate etc.
Preferred acid in these bronsted lowry acids and bases bronsted lowries, more preferably mineral acid or the organic acid of molecular weight more than 100.
Utilize the processing of acid and/or alkali, implement to make the particle before handling to contact with suitable method with acid and/or alkali, specifically be that the particle before handling is dispersed in acid and/or the aqueous slkali, subsequently, can isolate compound particle from acid and/or aqueous slkali, acid and/or aqueous slkali also can be aqueous solutions, use the solution that has mixed water-miscible organic solvents such as ethanol, the affinity of compound particle surface and liquid can be improved, more effective processing can be carried out.The blending ratio of water and organic solvent, in weight ratio, water: organic solvent=100: 0～20: 80.
The amount of used acid and/or alkali in the processing is suitably 0.1～2 mole doubly with respect to the zinc oxide in the particle before handling.The acid in the Treatment Solution and/or the concentration of alkali can suitably be regulated, and are preferably 0.01～6mol/L, 0.1～2mol/L more preferably, consider from dissolving more selectively, in the processing time, be preferably the short time near particle surface partial oxidation zinc aspect, preferred 1 minute～10 hours, more preferably 10 minutes～5 hours, treatment temperature just could so long as particle fusion or condensation temperature are following, be not particularly limited, can suitably set according to processing time and zinc oxide removal amount.
The removal amount of the zinc oxide in the processing is preferably to remove the condition of handling zinc oxide 1～50 weight % that contains in the preceding particle.The zinc oxide clearance can be measured by the calcination recrement of compound particle before and after handling, and as required, also can utilize the additive methods such as ICP luminesceence analysis of filtrate.
The zinc oxide containing ratio of handling in the compound particle of back is preferably 1～70 weight %, 5～50 weight % more preferably, preferred especially 10～40 weight %.
[zinc oxide survival rate in the particle]
Compound particle of the present invention presents the active inhibition of very high zinc oxide, as its opinion scale, can use that the zinc oxide in the particle retains rate after the salt acid treatment.That is, zinc oxide is dissolving fully in acid water, and character is cleaned compound particle with acid water thus, measures the zinc oxide amount, compares before and after acid water is cleaned, and calculates survival rate, thus the surface activity inhibition is estimated.After the compound particle salt of the present invention acid treatment, the survival rate of zinc fluoride in the particle, method is measured shown in the concrete available following test example 1.When the zinc oxide survival rate was near 100 weight % in the particle after the salt acid treatment, the activity of expression zinc oxide was inhibited.
Compound particle of the present invention, the survival rate of zinc oxide in the particle after the salt acid treatment is preferably more than 50 weight %, more preferably more than the 70 weight %, further more than the preferred 80 weight %, more than the preferred especially 90 weight %, the emulsifying goods of oil type in the water (O/W) can be stablized use.
For trying to achieve the zinc oxide effective ingredient of salt acid treatment rear oxidation zinc survival rate, the calcination recrement of available compound particle is measured, and as required, also can utilize the additive methods such as ICP luminesceence analysis of filtrate.
[ultraviolet-shielding type and the transparency]
Compound particle of the present invention preferably has the excellent ultraviolet-shielding type and the transparency simultaneously.Yardstick as this evaluation, be that compound particle is dispersed in the silicone oil, and in the quartz ampoule of the optical length 50 μ m that pack into, seeing through spectrum with spectrophotometric determination, the transmitance difference delta T of the 550nm wavelength of use visible region and the 350nm wavelength of ultraviolet range is effectively.Δ T is big more, can think to have simultaneously the character of the good ultraviolet-shielding type and the transparency.
The mixing ratio of silicone oil and compound particle with respect to 100 weight portion silicone oils, is got 1 weight portion with compound particle with zinc oxide.Preferably use SI-UGE (flower king (strain) system, alkyl glycerylether modified silicone) as silicone oil.This difference delta T is preferably more than 30%, more preferably more than 40%, particularly preferably in more than 50%.
[cosmetic]
In the cosmetic of the present invention, contain the amount of compound particle of the present invention, can suitably select, do not have particular determination, be preferably 0.1～50 weight %, more preferably 1～30 weight % according to the purpose of this cosmetic.
The form of cosmetic of the present invention does not have particular determination, can be in emulsified cosmetic preparation, oil-based cosmetic material, spraying cosmetic, stick-shaped cosmetic material, aqueous cosmetic, the film like cosmetic etc. of oil type in water in oil or the water any.The kind of cosmetic of the present invention does not have particular determination, Pack is for example arranged, foundation cream, lipstick, rouge, eye shadow, mascara, eyeliner, the eyebrow cosmetic, nial polish, change make-up water, cold cream (cold cream), hand cream, skin cleaning agent, softnessizationization make-up product, the nutrition cosmetic, the convergence cosmetic, skin-whitening cosmetics, wrinkle improves cosmetic, the anti-aging cosmetic, clean and use cosmetic, antiperspirant, remove skin cosmetics such as fetid sweat agent, shampoo, hair rinse, conditioning hairdressing, setting agent, hair cosmetic compositions such as hair growth promoter, preferably can bring into play ultraviolet shielding effect, the cosmetic of the hidden effect of skin is more preferably as cosmetic, sunscreen (Sunscreen), the substrate cosmetic uses.
Cosmetic of the present invention can contain alcohol.As alcohol, can enumerate carbon numbers such as ethanol, glycerol, 1,3 butylene glycol, propylene glycol, Sorbitol and be 1～6 1 valency or multivalence alcohol, wherein, 1 valency alcohol preferred alcohol.The use level of alcohol is preferably 5～30 weight %, 1～50 times of weight of compound particle weight more preferably of the present invention in the cosmetic of the present invention.
In the cosmetic of the present invention,, in the scope of not damaging effect of the present invention,, also can suitably cooperate normally used other compositions according to the form of above-mentioned cosmetic, kind etc. as the cosmetic composition.
As such cosmetic composition, body pigments such as Muscovitum, Talcum, sericite, Kaolin, nylon powder, polymethyl Silsesquioxane, barium sulfate are for example arranged; Solid pigments such as titanium oxide, zinc oxide, oxysome; These powder body are carried out the powder body of surface-hydrophobicized processing such as silicone-treated, metallic soap processing, the processing of N-acyl glutamic acid; Hydro carbons such as the paraffin of solid, shaped or liquid, microwax, vaseline, ceresin (ceresin), ceresine (ozacerite), montan wax; Vegetative grease, animal raw fat or waxes such as Fructus Canarii albi, ceresine, Brazil wax, lanoline, spermaceti; Stearic acid, Palmic acid, oleic acid, glyceryl monostearate, glycerol distearate, glycerin mono-fatty acid ester, isopropyl myristic acid ester, fatty acid or its esters such as Emerest 2310, butyl stearate; Senior alcohols such as spermol, stearyl alcohol, palmityl alcohol, hexyl dodecanol; Absorption or viscosifier such as Poise C-80M, carboxybetaine type polymer, cationization silicone; The multivalence alcohols of Carboxymethyl Chitin such as ethylene glycol, Sorbitol; The emulsifying agent that silicone oil such as polyether modified silicone, polyethers, alkyl-modified silicone, glycerin ether modified silicone are used; Viscosifier such as methylcellulose, ethyl cellulose, carboxymethyl cellulose, polyacrylic acid, Tragacanth (tragacanth), agar, gelatin; Antiperspiration agents such as polymeric aluminum chloride, aluminum chloride, aluminum sulfate, alkaline aluminium bromide, aluminium phenolsulfonate, alkaline silver iodide; Antibacterial such as 3,4,4 one Amolden MCM 400s (TCC), benzalkonium chloride, benzethonium chloride, alkyl trimethylammonium chloride, resorcinol, phenol, sorbic acid, salicylic acid, Perchlorobenzene; Moschus, scatol (skatole), Fructus Citri Limoniae oil, Essential lavender oil, absolute oil (absolute), jasmine, vanillin, benzoin, screening agent such as benzyl acetate, menthol in addition, also has emulsion stabilizer, chelating agen, ultraviolet screening agent, pH regulator agent, antiseptic, pigment, whitening agent, easing pain and diminishing inflammation agent, town's active ingredient such as agent, disinfection sanitizer, astringent, skin soft agent, hormone preparation of itching; Water; Surfactant, W/O or O/W type emulsifying agent, spice etc.
Embodiment
Following examples are that enforcement of the present invention is told about, and embodiment is the description to example of the present invention, but do not limit invention.
" % " " part " in the example if do not particularly point out, is meant " weight % " and " weight portion " respectively.The fusing point of polyolefin resin, the value of measuring by JIS K0064:1992.
Embodiment 1 (manufacturing of particle A)
Use Mitsui High wax HW-220MP (Mitsui Chemicals (strain) system, polyethylene, molecular weight 2000,107 ℃ of fusing points, degree of crystallinity 65%) as polyolefin resin, use FINEX-50S-LP2 (average primary particle diameter 0.02 μ m, silicone are handled zinc oxide, boundary's chemistry (strain) system) as zinc oxide, blending ratio (HW-220MP:FINEX-50S-LP2) mixes at 70: 30 by weight, use 100 ℃ of extruder PCM30 ((strain) pond shellfish system), spiral rotation number 200rpm, barrel temperatures, with charging in 10kg/ hour, and carry out mixing.Then use the prilling granulator of following condition, the melting mixing thing of polyethylene and zinc oxide is sprayed in 25 ℃ the gas phase, cooling, reclaim with compound particle, remove oversize grain with sieve, the average particle size that obtains is 3.3 μ m, utilizes that zinc oxide contains promising 29 weight % in the compound particle that the calcination recrement measures.
The condition of＜prilling granulator 〉
Nozzle: 4 fluid tips, linear type (the rugged motor of rattan (strain) system)
Mixing thing temperature: 150 ℃
Mixing thing liquor charging amount: 5ml/ minute
Assist gas temperature: 500 ℃
Assist gas flow: 50L/ branch
Embodiment 2 (manufacturing of particle B)
As polyolefin resin, use Mitsui High wax HW-220MP (Mitsui Chemicals (strain) system, polyethylene, molecular weight 2000,107 ℃ of fusing points, degree of crystallinity 65%) and Mitsui High waxHW-100MP (Mitsui Chemicals (strain) system, polyethylene, molecular weight 900,116 ℃ of fusing points, degree of crystallinity 90%); As zinc oxide, use the FINEX-50S-LP2 (zinc oxide that average primary particle diameter 0.02 μ m, silicone are handled, boundary's chemistry (strain) system), with weight blending ratio (HW-220MP: HW-100P: FINEX-50S-LP2) mix at 35: 35: 30, in addition, operate identical with embodiment 1, handle, reclaim compound particle, the degree of crystallinity of resinous principle is 77.5%, remove thick particle with sieve, the average particle size that obtains is 3.7 μ m, utilizes that zinc oxide content is 29 weight % in the compound particle that the calcination recrement measures
Comparative example 1 (manufacturing of particle C)
Remove as polyolefin resin, use Mitsui High wax HW-100P (Mitsui Chemicals (strain) system, polyethylene, molecular weight 900,116 ℃ of fusing points, degree of crystallinity 90%) outside, to handle with embodiment 1 identical operations, reclaim compound particle, remove oversize grain with sieve, the average particle size that obtains is 2.8 μ m, utilizes that heat-flash row are retained to divide that zinc oxide content is 30 weight % in the compound particle of measuring.
Comparative example 2 (manufacturing of particle D)
Remove as polyolefin resin, use C105 (シ ユ one マ Application サ ゾ one Le society, polyethylene, molecular weight 1300, fusing point more than 100 ℃, degree of crystallinity 88%) outside, to handle with embodiment 1 identical operations, reclaim compound particle, remove oversize grain with sieve, the average particle size that obtains is 3.4 μ m, utilizes that oxidation content is 29 weight % in the compound particle that the calcination recrement measures.
Comparative example 3 (manufacturing of particle E)
With the high density silicon dioxide layer zinc oxide fine particles sub-surface is sealed, form the ultra-fine particles of zinc oxide of nonactive type, use the particle of FINEX-K2-LP2 (boundary's chemistry (strain) system, zinc oxide composition 75%) as this comparative example.
Comparative example 4 (manufacturing of particle F)
Following method, preparation contains the co-polymer particle (mean diameter is 10.9 μ m, and zinc oxide content is 14 weight %) of the methyl methacrylate ethylene glycol methacrylate of zinc oxide fine particles.
(1) manufacturing of the sub-dispersion liquid of zinc oxide fine particles
Following each material is mixed, carry out 10 hours dispersion treatment, obtain the sub-dispersion liquid of zinc oxide fine particles with ball mill.
25 parts of micropartical zinc oxide
(FINEX-75, boundary's chemistry (strain) system, mean diameter 0.02 μ m)
69 parts of methyl methacrylates (resin monomer)
6 parts of dialkyl succinate sodium sulfonates
(Bellex OT-P flower king (strain) system, dispersant)
(2) manufacturing of resin particle
By shown below, resin monomer phase and water are mixed, it in homogenizer, was stirred 5 minutes with 8000rpm, the adjustment monomer drips and is about 5 μ m.Then with this split-up in reaction unit with blender and thermometer, be warmed up to 55 ℃, the beginning polymerization.In polymerization under this temperature after 5 hours, cool to room temperature separates the resin particle that obtains with suction filtration, with an amount of warm water cleaning, follows with behind the methanol cleaning, 55 ℃ of dryings 10 hours, makes resin particle.
＜resin monomer phase 〉
(3) 48 parts of the sub-dispersion liquids of zinc oxide fine particles
52 parts of methyl methacrylates (resin monomer)
20 parts of ethylene glycol methacrylates
(NK ESTER 1G, Xin Zhong village chemical industry (strain) system, cross-linking agent)
2,2-azo two-2,0.2 part of 4-methyl pentane nitrile (polymerization initiator)
＜water 〉
500 parts of ion exchange waters
10 parts of polyvinyl alcohol
(EG-30, Japanese synthetic chemical industry " (strain) system, saponification degree 87%).
Test example 1: (survival rate of the interior zinc oxide of particle after the salt acid treatment) tested in pickling only
25mL 0.5mol/L aqueous hydrochloric acid solution and 25mL ethanol are mixed, the particle that obtains in embodiment and the comparative example is mixed with the amount that zinc oxide is equivalent to 1g, pack in the serpentine pipe of 100mL, and being arranged on (the long 10cm of stroke, reciprocal 100 times/minute) on the vibrating machine, (25 ℃) vibration is 2 hours under the room temperature, PTFE membrane filter with aperture 0.5 μ m carries out filtration under diminished pressure, reuse ethanol is cleaned, and with 70 ℃ of air driers dryings after 12 hours, obtains the particle after the salt acid treatment.This particle was handled 2 hours down at 800 ℃, with the calcination recrement that obtains as the salt acid treatment after zinc oxide amount in the particle, calculate the interior zinc oxide survival rate of particle after the salt acid treatment with following formula (I).The result is as shown in table 1.
Zinc oxide survival rate (%)=(A2/A1) * 100 after the salt acid treatment in the particle
(I) wherein
A1: the zinc oxide content (%) before the salt acid treatment in the particle
A2: the zinc oxide content after the salt acid treatment in the particle (%)
Test example 2: formulation stability test (anti-UV stability of formulation)
Pack into 79.12g Purified Water, 0.3g acrylic compounds viscosifier (ETD2020, BFGoodrich society system), 0.2g acrylic compounds viscosifier (pemulen TR-2, daylight chemical ' s (strain) system) and 0.2g methyl butex, all mix, then add 0.18g triethanolamine aqueous solution (effective ingredient 89%), further mix, be modulated into to estimate and use basic glue.
In the 100ml beaker, mix the evaluation particle and the 0.3g ethanol that contain 0.3g zinc oxide weight, be uniformly dispersed with ultrasonic dispersing machine.Mix 16.0g and estimate and use basic glue, use the quick runner dispersion machine, the whole stirring until evenly, room temperature (25 ℃) environment was preserved 3 hours down, with it as evaluation glue.
Use Brookfield viscometer, under 25 ℃, the condition determination of 6rpm, measure the evaluation that obtains viscosity, and observe outward appearance with glue.Cooperated the evaluation of the compound particle of embodiment to be high viscosity with glue, the particle homodisperse, but cooperated the evaluation glue of the particle of comparative example, viscosity drops to be measured below the lower limit 1000mPas, when detecting by an unaided eye, finds liquid and separate particles.
With having cooperated the evaluation glue of embodiment particle, under 50 ℃ of environment, preserved 21 days.Still keep viscosity after the preservation, find no fluid separation applications in appearance.(II) obtains the viscosity rate of change according to following formula, and the result is as shown in table 1.
Viscosity rate of change (%)=(η 2/ η 1) * 100 (II)
Wherein:
η 1: viscosity (mPas) when estimating the preparation of glue
η 2: viscosity (mPas) after the preservation of evaluation glue
Test example 3: optical characteristics test (evaluation of the ultraviolet-shielding type and the transparency)
For 100 parts of SI-UGE (flower king (strain) system, alkyl glycerylether modified silicone), the particle that embodiment and comparative example are obtained is equivalent to 1 part amount with zinc oxide and mixes, and uses scraper to carry out homodisperse.This mixture is packed in the quartz ampoule of optical length 50 μ m, use spectrophotometer (Shimadzu Seisakusho Ltd.'s (strain) system.UV-2550), calculate the difference Δ T of transmitance of the wavelength of 550nm and 350nm, the result is as shown in table 1.Any compound particle all has the good ultraviolet-shielding type and the transparency, demonstrates as the material of making up to have good performance.
Table 1
Embodiment 3 (manufacturing of particle G)
As thermoplastic resin, use Mitsui High wax HW-220MP (Mitsui Chemicals (strain) system, polyethylene, molecular weight 2000,107 ℃ of fusing points, degree of crystallinity 65%), as zinc oxide, use FINEX-50S-LP2 (average primary particle diameter 0.02 μ m, the zinc oxide that silicone is handled, boundary's chemistry (strain) system), weight mixing ratio 70/30 with polyethylene/zinc oxide is mixed, use extruder PCM30 (strain) pond shellfish system) screw rod rotation number 200r/min, 100 ℃ of feeding rate 10kg/ of cylindrical shell humidity hours, carry out mixing.Then, as spray nozzle, use linear type 4 fluid tips (Micro Mist Dryer MDL-050C, the rugged motor of rattan (strain) system), under 150 ℃, Capacity Ratio with spraying nitrogen gas/mixing thing is 21000/1, is sprayed in 25 ℃ the gas phase and cooling, reclaims with compound particle, the particle volume mean diameter that obtains is 12.4 μ m, and the following particle containing ratio of particle diameter 5 μ m is 15.8 volume %.
Embodiment 4 (manufacturing of particle H)
Except as spray nozzle, use outside pencil-type 3 fluid tips (Micro Mist DryerMDL-050C, the rugged motor of rattan (strain) system), to handle with embodiment 3 identical operations, reclaim compound particle, the particle volume mean diameter that obtains is 8.4 μ m, and the following particle containing ratio of particle diameter 5 μ m is 27.1 volume %.
Embodiment 5 (manufacturing of particle I)
Except as thermoplastic resin, use Mitsui High wax HW-220MP (Mitsui Chemicals (strain) system, polyethylene, molecular weight 2000,107 ℃ of fusing points, degree of crystallinity 65%) and Mitsui High wax HW-100P (Mitsui Chemicals (strain) system, polyethylene, molecular weight 900,116 ℃ of fusing points, degree of crystallinity 90%); As zinc oxide, use FINEX-50S-LP2 (average primary particle diameter 0.02 μ m, the zinc oxide that silicone is handled, boundary's chemistry (strain) system); Outside the weight mixing ratio 35/35/30 of HW-220MP/HW-100P/ zinc oxide is mixed, with with embodiment 4 in identical operations handle, reclaim compound particle, the particle volume mean diameter that obtains is 5.4 μ m, and the following particle containing ratio of particle diameter 5 μ m is 52.1 volume %.
Embodiment 6 (manufacturing of particle J)
Except the Capacity Ratio with spraying nitrogen gas/mixing thing is taken as 10000/1, handle with identical operations among the embodiment 5, reclaim compound particle, the particle volume mean diameter that obtains is 5.8 μ m, the following particle containing ratio of particle diameter 5 μ m is 50.2 volume %
Spray condition and the result of embodiment 3～6 are as shown in table 2.
Table 2
| |
|
|
Embodiment 6 | |
| |
4 fluid tip |
3 fluid tip pencil- |
3 fluid tip pencil- |
3 fluid tip pencil-type |
| Spray condition spraying nitrogen/mixing thing (Capacity Ratio) vapo(u)rizing temperature (℃) viscosity (mPas) during spraying | 21000/1 150 80 | 21000/1 150 80 | 21000/1 150 50 | 10000/1 150 50 |
| The particle containing ratio (volume %) that compound particle volume average particle size (μ m) |
12.4 15.8 | 8.4 27.1 | 5.4 52.1 | 5.8 50.2 |
Embodiment 7 (manufacturing of particle K)
With polyethylene (molecular weight 900, trade name: HW-100P/ Mitsui Chemicals (strain) is made) and the zinc oxide (zinc oxide that silicone is handled, average primary particle diameter 0.02 μ m, trade name: FINEX50S-LP2/ circle chemistry), mix at 70: 30 with weight rate, use extruder PCM30 ((strain) pond shellfish system), carried out mixing with screw rod rotation number 200rpm, 30 ℃-60 ℃-100 ℃-100 ℃-100 ℃-100 ℃-100 ℃ of barrel temperatures, feeding rate 10kg/ hour.Use molten atomizing cooling granulation device,, obtain the particle K of mean diameter 3.8 μ m, utilize that zinc oxide content is 29% in the particle that the calcination recrement measures the mixing thing that obtains particlized under the following conditions.
The condition of＜prilling granulator 〉
Nozzle: 4 fluid tips, linear type (the rugged motor of rattan (strain) system)
Mixing thing temperature: 150 ℃
The mixing thing amount of infeeding: 5mL/ minute
Assist gas temperature: 500 ℃
Assist gas flow: 50L/ minute
Embodiment 8 (manufacturing of particle L)
Except using molecular weight 1300 (trade name: C105/ シ ユ one マ Application サ ゾ one Le society) as polyethylene, carry out the operation same with embodiment 7, obtain the particle L of mean diameter 3.4 μ m, utilize that the zinc oxide amount is 29% in the particle that the calcination recrement measures
Embodiment 9 (manufacturing of particle M)
In 200mL 0.1% single myristyl potassium phosphate (MAP-40H/ flower king (strain) system) aqueous solution, mix 3.0g particle K, use homogenizer,, carry out 3 minutes dispersion treatment with 5000rpm, PTFE membrane filter with aperture 0.45 μ m, dispersion liquid is carried out filtration under diminished pressure, use the 100mL ion exchange water successively, 50mL ethanol, 50mL ethanol filters clean, obtains the alcohol slurry of anionic surfactant's item for disposal of particle K.
Embodiment 10 (manufacturing of particle N)
Use particle L to replace particle K; as the anionic surfactant; outside the cocoyl N-methyltaurine (trade name: ニ Star コ Le CMT-30/ daylight chemical ' s (strain) system) of use 0.1%; carry out 9 identical operations, obtain the ethanol serosity of anionic surfactant's item for disposal of particle L with embodiment.
Test example 4
For the particle of embodiment 9 and 7, estimate fitment stability in order to following method, the result is as shown in table 3.
＜fitment stability assessment method 〉
The 79.12g Purified Water of packing into, 0.3g acrylic compounds viscosifier (ETD2020, BFGoodrich society system), 0.2g acrylic compounds viscosifier (Pemulen TR-2, daylight chemical ' s (strain) system), the 0.2g methyl butex, integral body mixes to evenly, then add 0.18g triethanolamine water (effective ingredient 89%), restir is mixed to evenly whole, is modulated into to estimate to use basic glue.
In 20mL glass tubing container, the evaluation particle and the 1.7g ethanol of packing into and containing the 0.2g zinc oxide, be uniformly dispersed with ultrasonic dispersing machine, add the basic glue of 3.0g evaluation, use the pencil-type blender, be stirred to all evenly, obtain estimating glue, should estimate glue and be kept in 50 ℃ of environment, and measure appearance and separate the needed times for two layers.
Table 3
| Zinc oxide amount (%) in the particle | Up to the time that separation needs occurring | |
| Embodiment 9 | 29 | More than 30 hours |
| Embodiment 7 | 29 | Below 3 hours |
Test example 5
For the particle of embodiment 10 and 8, estimate fitment stability in order to following method, the result is as shown in table 4.
＜fitment stability assessment method 〉
Prepare the anti-UV glue of O/W type in the following order, in its 100mL serpentine pipe of packing into, preserved 7 days and 14 days in 50 ℃ of temperature chambers, the viscosity of measuring respectively between storage life changes,
The preparation order of the anti-UV glue of O/W type
1) with 95 degree synthesizing alcohols (32.5g), p-methoxycinnamic acid 2-Octyl Nitrite (8.5g) mixes, as a liquid.
2) Purified Water (39.5g), disodium edetate (0.01g) are mixed, then utilize the quick runner dispersion machine, under agitation (the acrylic compounds viscosifier, 0.3g) mix homogeneously is as b liquid with carbon ball ETD2020.
3) utilize the quick runner dispersion machine with 95 degree synthesizing alcohols (9.0g), evaluation particle (7.0g) mix homogeneously, as c liquid.
4) under propeller agitation, (the tackify emulsifying agent 0.60g) mixes, and then slowly mixes c liquid, fully stirs, and obtains d liquid with a liquid, b liquid, acculin22.
5) with dispersion machines such as homogenizers d liquid is disperseed, be mixed with visual uniform O/W dispersion liquid.
6) under propeller agitation, in d liquid, mix the propeller mixed liquor of 2-amino-2-methyl-1-propanol (0.08g) and Purified Water (0.5g), then mix concentrated glycerin (0.5g).
The composition of the anti-UV glue of O/W type
95 degree synthols 41.50%
P-methoxycinnamic acid 2-Octyl Nitrite 8.50
Estimate particle 7.00
Carbon ball ETD2020 (BFGoodrich society system) 0.30
acculin22(ROHM AND HASS COMPANY) 0.60
Cosmetic concentrated glycerin 0.50
2-amino-2-methyl-1-propanol 0.08
Disodium edetate 0.01
The Purified Water balance
The mensuration of viscosity
Before the mensuration, fully vibrate with hands the serpentine pipe of the anti-UV glue of O/W type be housed, in being set at 25 ℃ tank, soak 30 minutes after, measure viscosity with Brookfield viscometer.Condition determination is taken as 30rpm, No. 4 rotors, 1 minute.Viscosity after cooperating is taken as at 100% o'clock, as the viscosity rate of change, utilizes following formula to obtain respectively the viscosity ratio of 50 ℃ of following preservations after 7 days or 14 days.
Viscosity rate of change (%)=(η 2/ η 1) * 100
Wherein:
η 1: the viscosity (mPas) after anti-UV glue has just cooperated
η 2: the viscosity (mPas) after anti-UV glue is preserved
Table 4
Embodiment 11 (manufacturing of particle O)
With polyethylene (molecule 1 300, C105/ シ ュ one マ Application サ ゾ one Le society) and the zinc oxide (zinc oxide that silicone is handled trade name:, average primary particle diameter 0.02 μ m, trade name: FINEX50S-LP2/ circle chemistry), mix at 70: 30 with weight rate, use extruder PCM30 ((strain) pond shellfish system), with screw rod rotation number 200rpm, 30 ℃-60 ℃-100 ℃-100 ℃-100 ℃-100 ℃-100 ℃ of barrel temperatures, feeding rate 10kg/ hour carry out mixing.Use molten molten atomizing cooling granulation device,, obtain the particle of mean diameter 3.4 μ m, utilize that zinc oxide content is 30% in the particle that the calcination recrement measures the mixing thing that obtains particlized under the following conditions.
The condition of＜prilling granulator 〉
Nozzle: 4 fluid tips, linear type (the rugged motor of rattan (strain) system)
Mixing thing temperature: 150 ℃
The mixing thing amount of infeeding: 5mL/ minute
Assist gas temperature: 500 ℃
Assist gas flow: 50L/ minute
Embodiment 12 (manufacturing of particle P)
Use particle O, make 250mL, the phosphoric acid solution of 0.5mol/L is (as solvent composition, water: ethanol=50: 50 (volume ratio)), to wherein mixing 15g particle O, in the polyethylene can of packing into, with vibrating machine (the long 10cm of stroke, reciprocal 100 times/minute) vibration 4 hours.
After the vibration, in separatory funnel, pack into particle O dispersion liquid and 1000mL ion exchange water, fully vibration mixes.Because particle O floats on the liquid level, so remove the liquid that sub-cloud does not contain particle O, add the 1000mL ion exchange water again, only remove lower floor's liquid.Repeat this operation, reach till 6～8 up to the pH that records subnatant with pH reagent paper (pH reagent paper UNIV, ADVANTEC Japan system), use 3.0 μ m membrane filters that the particle O aqueous dispersions that obtains is carried out sucking filtration, intensive drying under 60 ℃ of reduced pressure atmosphere, obtain the phosphoric acid item for disposal of particle O, utilize after the processing that the calcination recrement measures that zinc oxide content is 17% in the compound particle.
Embodiment 13 (manufacturing of particle Q)
Use particle O, use the succinic acid solution (solvent composition of 0.5mol/L, water: ethanol=50: 50 (volume ratio)) replace outside the phosphoric acid, equally with embodiment 12 carry out acid treatment, obtain the succinic acid item for disposal of an O, utilize after the processing that the calcination recrement measures that zinc oxide content is 16% in the compound particle.
To the particle of embodiment 11,12,13, carry out the fitment stability test as follows, the result is as shown in table 5.
＜fitment stability test 〉
In the following order, the anti-UV glue of oil type in its 100mL serpentine pipe of packing into, was preserved for 3 weeks in 50 ℃ of temperature chambers in the modulation water, and the viscosity of measuring between storage life changes.
The modulation order of the anti-UV glue of oil type in the water
1) 95 degree synthesizing alcohols (32.5g), p-methoxycinnamic acid 2-Octyl Nitrite (8.5g) are mixed, as a liquid.
2) with Purified Water (39.5g), disodium edetate (0.01g) mixes, and then uses the quick runner dispersion machine, and under agitation (the acrylic compounds viscosifier, 0.3g) mix homogeneously is as b liquid with carbon ball ETD2020
3) with 95 degree synthesizing alcohols (9.0g), evaluation particle (7.0g), with quick runner dispersion machine mix homogeneously, as c liquid.
4) under the propeller agitation, (the tackify emulsifying agent 0.60g) mixes, and then slowly mixes c liquid, fully stirs, and obtains d liquid with a liquid, b liquid, acculin 22.
5) with dispersion machines such as homogenizers d liquid is disperseed, be mixed with visual uniform O/W dispersion liquid.
6) under propeller agitation, in d liquid, mix the mixed liquor of 2-amino-2-methyl-1-propanol (0.08g) and Purified Water (0.5g), then mix concentrated glycerin (0.5g).
The composition of the anti-UV glue of oil type in the water
95 degree synthols 41.50%
P-methoxycinnamic acid 2-Octyl Nitrite 8.50
Estimate particle 7.00
Carbon ball ETD2020 (BFGoodrich society system) 0.30
Acculin 22(ROHM AND HASS COMPANY) 0.60
Cosmetic concentrated glycerin 0.50
2-amino-2-methyl-1-propanol 0.08
Disodium edetate 0.01
The Purified Water balance
The mensuration of viscosity
Fully vibrate with hands before measuring the serpentine pipe of the anti-UV glue of oil type in the water be housed, in setting 25 ℃ tank, soak 30 minutes after, measure viscosity with Brookfield viscometer, condition determination is taken as 30rpm, No. 4 rotors, 1 minute.Viscosity after cooperating is taken as at 100% o'clock, the viscosity ratio after 50 ℃ of 3 weeks of following preservation as the viscosity rate of change, is obtained by following formula.
Viscosity rate of change (%)=(η 2/ η 1) * 100
Wherein:
η 1: the viscosity (mPas) after anti-UV glue has just cooperated
η 2: the viscosity (mPas) after anti-UV glue is preserved
Table 5
| The amount of the zinc oxide in the particle (%) | Viscosity rate of change (%) | |
| Embodiment 12 | 17 | 81 |
| Embodiment 13 | 16 | 82 |
| Embodiment 11 | 30 | 22 |
Claims (7)
1. a compound particle is characterized in that, contains degree of crystallinity at sour modified poly ethylene and zinc oxide below 80%, obtain with fusion dispersion method or molten atomizing cooling method,
The weight ratio of sour modified poly ethylene and zinc oxide is sour modified poly ethylene/zinc oxide=99/1～30/70 in the compound particle.
2. compound particle as claimed in claim 1 is characterized in that, volume average particle size is 0.5～30 μ m.
3. compound particle manufacture method as claimed in claim 1, it is characterized in that, is after mix sour modified poly ethylene/zinc oxide=99/1～30/70 with sour modified poly ethylene and zinc oxide with weight ratio, under the temperature more than the softening temperature of sour modified poly ethylene, this mixture is sprayed in the cooling medium, with cooling curing.
4. compound particle manufacture method as claimed in claim 3 is characterized in that, uses the above nozzle of 3 fluids to spray.
5. compound particle manufacture method as claimed in claim 4 is characterized in that, the above nozzle of 3 fluids is linear type nozzle or pencil-type nozzle.
6. described compound particle manufacture method as claimed in claim 3 is characterized in that, when the mixture of sour modified poly ethylene and zinc oxide was sprayed, the Capacity Ratio of spray gas/mixture was 1000/1～100000/1.
7. cosmetic that contains the described compound particle of claim 1.
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