CA2183622A1 - Method of improving ultraviolet radiation absorption of a composition - Google Patents
Method of improving ultraviolet radiation absorption of a compositionInfo
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- CA2183622A1 CA2183622A1 CA002183622A CA2183622A CA2183622A1 CA 2183622 A1 CA2183622 A1 CA 2183622A1 CA 002183622 A CA002183622 A CA 002183622A CA 2183622 A CA2183622 A CA 2183622A CA 2183622 A1 CA2183622 A1 CA 2183622A1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y5/00—Nanobiotechnology or nanomedicine, e.g. protein engineering or drug delivery
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- A61K8/8141—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- A61K8/8152—Homopolymers or copolymers of esters, e.g. (meth)acrylic acid esters; Compositions of derivatives of such polymers
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P17/00—Drugs for dermatological disorders
- A61P17/16—Emollients or protectives, e.g. against radiation
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
- A61Q17/04—Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
- A61K2800/41—Particular ingredients further characterized by their size
- A61K2800/413—Nanosized, i.e. having sizes below 100 nm
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
- A61K2800/54—Polymers characterized by specific structures/properties
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Abstract
A method is disclosed for improving the UV radiation absorption of a composition containing a UV radiation absorbing agent by adding from about 0.1 weight percent to about 50 weight percent of latex particles, based on total weight nonvolatiles. The latex particles contain a void and have a particle size of from about 100 nm to about 380 nm.
Description
METHOD OF IMI'ROVING ULTRAVIOLET
RADIATION ABSORPTION OF A COMPOSITION
This is a ~ontinll~tion-in-part of application Serial No. 08/203,178 filed on February 28,1994.
FIELD OF THE INVENTION
This invention relates to a method of improving absorption of ultraviolet radiation by adding voided latex particles to a composition containing at least one ultraviole~ radiation absorbing agent.
BACKGROUND OF THE INVENTION
Six percent of the solar energy reaching the earth's surface is ultraviolet (UV) radiation having a wavelength of 290-400 nanometers (nm). This radiation has two components:
(1) 5.5/O UVA having a wavelength of 320-400 nm and (2) 0.5~1~o UVB having a wavelength of 290-320 nm.
While the UV portion of the solal~ energy is relatively small, it induces nearly 99/O of all the side effects of sunlight. UVB radiation, for example, is responsible for producing sunburn, aging and cancer of the skin. WA
radiation, for example, causes direct tanning and erythema (abnormal redness) and contributes to aging of the skin.
By avoiding exposure to sunlight, people can avoid the serious effects caused by the UV radiatior~. However, because of the nature of their work, some people cannot avoid exposure to the sun. In addition, others voluntarily expose their skin to the sun to tan, sometimes to extremes. Therefore, protection against the harmful effects of the sun is important.
Protection from these harmful effects of UV radiation exposure is available in the form of both topically applied formulations containing at least one physical blocker, or at least one chemical absorber, or combinations thereof. Physical blockers include active ingredients such as red petrolatum, titanium dioxide and zinc oxide. Chemical absorbers include active ingredients, such as p~ra-aminobenzoic acid (more commonly known as PABA), which are generally transparent when applied and act by absorbing UV radiation, offering selective protection against certain UV wave bands, d!epending upon the absorption spectrum of the particular active ingredient incorporated into the formulation.
The effectiveness of a sunscreen formulation is generally assessed by how well it protects the skin in terms of a Sun Protection Factor (SPF) which is defined as the ratio of the amount of energy required to produce a minimal erythema on sunscreen protected skin to the amount of energy required to produce the same level of erythema on unprotected skin.
A number of the chemical absorbers and physical blockers, herein after referred to as "UV radiation absorbing agents," typically used in sunscreen formulations have adverse toxicological effects. Therefore, it is desirable to reduce the level of U~ radiation absorbing agents present in a sunscreen formulation without reducing the level of plolt-lio,~.
One attempt to reduce the level of UV radiation absorbing agents in a sunscreen formulation is disclosed in U.S. Patent Number 4,804,531 to Grollier, hereinafter referred to as "Grollier." Grollier discloses adding to a cosmetic screening rrlmrrSi~iOn an aqueous ~licrrr~i~)n of water insoluble polymer particles where the polynller particles comprise a) an ionic polymer forming a core capable of being swollen, and b) a polymer forming a sheath at least partially encapsulating the core. The water insoluble polymer particles are disclosed to be film forming, to have a sheath glass transition temperature below 50 C, and to have an average particle size before swelling of from 70 nanometers (nm) to 4500 nm.
Grollier discloses that when the water insoluble polymer particles are added to a cosmetic screening composition at a level of from 0.1 to 10 weight percent, based on the total weight of the cosmetic screening composition, the absorption of U~ radiation in the cosmetic screening composition is increased.
Improving upon the teachings of Grollier, we have unexpectedly found that voided latex particles having certain particle sizes, increase the absorbance of UV radiation in a composition containing one or more UV
radiation absorbing agents.
SUMMARY O~F THE INVENTION
We have discovered a method for improving UV radiation absorption of a composition, comprising: adding to said composition from about 0.1 weight percent to about 50 weight percent of latex particles, based on total weight of nonvolatiles, wherein the composition comprises at least one UV radiation absorbing algent, and wherein the latex particles contain a void and have a particle size of from about 100 nm to about 380 nm .
BRIEF DESCRlrTrON OF Tr~E DRAWINGS
rn the drawings:
FIG. 1 is a UV radiation absorbance spectrum from a wavelength of 280-440 nm for compositions contAining no additives, solid latex particles and Yoided latex particles at a coating level of 5 microliters per square inch (Ill/in2). The active ingredients in the compositions are 2-ethylhexyl para-methoxycinnamate and menthyl alnthranilate. The additiYes are incorporated at a level of 5/O by weight, based on total weight nonvolatiles.
FIG. 2 is a UV radiation absorbance spectrum from a wavelength of 280-440 nm for compositions containing no additives and voided latex particles at a coating level of 10 111/in2. The active ingredients in the compositions are 2-ethylhexyl para-methoxycinnamate and menthyl anthranilate. The additives are incorporated at a level of 5/O by weight, based on total weight nonvolatiles.
FIG. 3 is a UV radiation absorbance spectrum from a wavelength of 280-440 nm for compositions t -)n~Ainin~ no additives, solid latex particles and voided latex particles at a coating level of 20 111/in2. The active ingredients in the compositions ale 2-ethylhexyl para-methoxyl-innAm~P
and menthyl anthranilate. The additives are incorporated at a level of 5%
by weight, based on total weight n.onvolatiles.
FIG. 4 is a UV radiation absorbance spectrum from a wavelength of 280-440 nm for compositions cont~ining no additives, solid latex particles and voided latex particles at a coating level of 40 ~LI/in2. The active ingredients in the compositions are 2-ethyl~exyl para-methoxycinnamate and menthyl anthranilate. The additives are incorporated at a level of 5%
by weight, based on total weight n.onvolatiles.
FIG. 5 is a graph showing falr 6 UV radiation absorbing compositions, the r~lA~ir nchip of the Sun Protection Factor (SPF) for the compositions (Y axis) versus the particle size, in nm, of voided latex particles contained in the composi~:ions (X axis). The voided latex particles (as solids) are incorporated in the compositions at a level of 10 weight percent, based on total weight non.volatiles. In addition to the voided latex particles, the compositions also contained, phenylben7imi(1A~n'^
sulfonic acid, a UV radiation absorbing agent.
` 4 21 83~
DETAILED DESCRI;PTION OF THE INVE~TION
The method of the invention improves the UV radiation absorption of a composition containing at least one UV radiation absorbing agent. The method of the present invention includes incorporating from about 0.1 weight percent to about 50 weight percent, and preferably from about 1 weiglllt percent to about 20 weight percent, based on total weight nonvolatiles, of voided latex particles to a composition containing at least one ultraviolet radiation absorbing agent.
As used herein, the term "UV radiation" includes both UVA and UVi3 radia tion.
The latex particles useful in the method of this invention have a particle size of from about 100 namometers (nm) to about 380 nm, preferably from about 150 nm to ~Ibout 375 nm, more preferably from about 190 nm to about 350 nm, and most preferably from about 251 nm to about 325 nm as measured by a Brookhaven Bl-90 photon correlation spectrometer.
For a given particle size, it is desirable to produce latex particles with a m~imllm void fraction as current processing techniques and particle integrity will permit. Preferably, l:he latex particles contain a void with a void fraction of from about 0.1% to about 50%, and more preferably from about 5% to about 50%. The void fractions are rlrt~rminrd by romrarinr the volume occupied by the latex particles after they have been rrlmr~rt,o~l from a dilute dispersion in a centrifuge to the volume of non-voided particles of the same composition.
The voided latex particles useful in the method of this invention are formed from a multistaged pa~ticle comprising at least one core polymer and at least one shell polymer. The core polymer and shell polymer may be made in a single polymerization step or in a sequence of polymerization steps.
The voided latex particles are prepared by conventional polymerization techniques such as, sequential emulsion polymerization, including those processes disclosed in U.S. Patents 4,427,836; 4,469,825;
4,594,363; 4,677,003; 4,920,160; 4,970,241, whose disclosures are incorporated herein by reference. The voided latex particles may also be prepared, for example, by polymerization techn~ques disc~osed in European Patent Application 0,267,726, European Patent Application 0,331,421, U.S. Patent 4,910,229, or U.S. Patent 5,157,084.
~, . 2 ~ 83622 The monomers used in the emulsion polymerization of the shell polymer of the voided latex particles preferably comprise one or more non-ionic ethylenically unsaturated monomer. Optionally, one or more monoethylenically unsaturated monomers containihg at least one carboxylic acid group may be polymerized in the shell.
The m~lnr~mPr.c which comprise the shell are selected to provide a glass transition temperature (Tg) in at least one shell which is high enough to s~lpport the void withitl the latex particle. Preferably the Tg of at least one shell is greater than 50 C, more preferably greater than 60 C, and most preferably greater than ~0 C as measured by differential scanning calorimetry.
The mt~nflmPrs used in the emulsion polymerization of the core polymer of the voided latex particles preferably comprise one or more monoethylenically unsaturated monomers containing at least one carboxylic acid group. Preferably, the core comprises at least 5 weight percent of the monoethylenically unsaturated monomers containing at least one carboxylic acid, based on total monomer weight of the core. The core polymer may be obtained, for example, by the emulsion homopolymerization of the monoethylenically unsaturated monomer containing at least one carboxylic acid group or by copolymerization of two or more of the monoethylenically unsaturated monomers containing at least one carboxylic acid group. Preferably, the monoethylenically unsaturated monomer containin~ at least one carboxylic acid group is copolymerized with one or more non-ionic ~that is, haYing no ionizable group) ethylenically unsaturated monomers.
The core polymer or shell polymer may optionally contain from about 0.1 weight percent to about ~0 weight percent, preferably about 0.1 weight percent to about 3 weight percent, based on the total monomer weight of tile core, of polyethylen;cally unsaturated monomer, such as ethylene glycol di(meth)acrylate, allyl (meth)acrylate, 1,3-butanediol di(meth)acrylate, diethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, or divinylbenzene. Alternatively, the core polymer or shell polymer may optionally contain from about 0.1 weight percent to about 60 weight percent, based on the total monomer weight of the core, of butadiene.
Suitable monoethylenically unsaturated monomers containing at least one carboxylic acid group include for example acrylic acid and methacrylic acid, acryloxypropionic acid, (meth)acryloxypropionic acid, 6 2t83622 itaconic acid, aconitic acid, maleic acid or anhydride, fumaric acid, crotonic acid, monomethyl maleate, monomethyl fumarate, and monomethyl itaconate. Acrylic acid and methacrylic acid are preferred.
Suitable non-ionic ethylenically unsaturated monomers include for example styrene, vinyltoluene, ethylene, vinyl acetate, vinyl chloride, vinylidene chloride, acrylonitrile, (meth)acrylamide, (C1-C20) alkyl or (C3-C20) alkenyl esters of (meth)acrylic acid, such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, benzyl (meth)acrylate, lauryl (meth)acrylate, oleyl (meth)acrylate, palmityl (meth)acrylate and stearyl (meth)acrylate. As used herein, the term "(meth)acrylic" is intended to serve as a generic expression embracing both acrylic and methacrylic.
The void of the latex particles is preferably produced by swelling the core with a swelling agent ~ in~ one or more volatile components.
The swelling agent permeates the shell to swell the core. The volatile components of the swelling agent can then be removed by drying the latex particles, causing a void to be fornled within the latex particles. Preferably, the swelling agent is an aqueous base. The aqueous base useful for swelling the core includes, for example, ammonia, ammr1nil'm hydroxide, alkali metal hydroxides, such as sodium hydroxide, or a volatile amine such as trimethylamine or trieth~lamine.
The voided latex particles may be added to the composition with the swelling agent present in the core When the latex particles are added to the composition with the swelling agent present in the core, the volatile components of the swelling agent will be removed upon drying of the composition. The voided latex pal-ticles may also be added to the composition after removing the volatile components of the swelling agent.
In addition to the voided la,tex particles, the composition improved by the method of the present inYention contains at least one UV radiation absorbing agent. The UV radiation absorbing agent may be incorporated into the composition at a level to produce a desired sun protection factor.
For example, the UV radiation abs~rbing agent may be added to the composition at a level of generally from about 0.1 weight percent to about 15 weight percent, based on the total weight of nonvolatiles in the composition.
The UV absorbing agents used in the method of this invention are conventional materials. Suitable UV radiation absorbing agents include, 21 836~2 for example, oxybenzone, dioxybenzone, sulisobenzone, menthyl anthranilate, para-aminobenzoic acid, amyl para-dimethyl~minot!Pn7o:-acid, octyl para-dimethylaminobenzoate, ethyl 4-bis (hydroxypropyl) para-aminobénzoate, polyethylene glycl~l (PEG-25) para-aminobenzoate, ethyl 4-bis (hydroxypropyl) aminobenzoate, rliPth~nnl~mine para-methyoxycinnamate, 2-ethoxyeth~l para-methoxycinnamate, ethylhexyl para-methoxyrinn~n~ ~P, octyl paramethoxyninn~m~P, isoamyl para-methoxycinnamate, 2-ethylhexyl 2-cyano-3,3-diphenyl-acrylate, 2-ethylhexyl salicylate, hnmomPn~h~l salicylate, glyceryl aminobenzoate, triethanolamine salicylate, digalloyl trioleate, lawsone with dihydroxyacetone, 2-phenylbenzin~idazole-5-sulfonic acid, benzylidine camphor, avobenzone, titanium dioxide, and zinc oxicle.
The composition improved by the method of this invention may also include other conventional ingredients used in UV absorbing compositions. For example, if the composition is used as a sunscreen, it may additionally include water, film forming materials, PmlllcifiPr~, water, ~molliPn~c, waterproofing agents, oils, stabilizers, thickeners, preservatives, perfume, colorants, insPr~ lPc, or humectants or combinations thereof. If the composition is used as a cosmetic, it may additionally include, for example, water, film forming materials, emulsifiers, softeners, emollients, ,:)ils, stabilizers, thickeners, preservatives, perfume, colorants, or pigments, or combinations thereof.
The composition improved by the method of this invention may be used in any application where protection from UV radiation is useful. For example, the improved composition may be used on human skin and hair, such as, for example personal care products, including, cosmetics, sunscreens, and hair care products. In addition, the method of this invention is also useful in improving the UV absorption and protection for coatings on plant life, plastics, ~ood, for example in the form of a clear varnish.
The method of this invention may be used to improve the UV
radiation absorption in either clear or pigmented formulations The method is particularly useful if a c~ear formulation is desired, such as a sunscreen forml~ n, because the addition of the voided latex particles having a particle size of less than about 300 nm does not significantly contribute to whiteness.
The method of this invention enables formulators to either increase the UV radiation absorbance of a given formulation or reduce the 8 21836~2 level of the UV radiation absorbinlg agent present in the form~ n while maintaining a given UV radiation absorbance.
The compositions improved by the method of this invention may be applied to the skin at coating volumes, for example, of from about 0.5 microliters per square centimeter to about 4 microliters per square cpntimetpr~
EXAMPLES
Some embodiments of the invention will now be described in detail in the following examples. The following abbreviations are used in the Examples:
MMA weight E~ercent methyl methacrylate BMA weight percent butyl methacrylate MAA weight percent methacrylic acid Sty weight F~ercent styrene ALMA weight percent allyl methacrylate pbw parts by weight For Examples 1 and 2, voidc~d latex particles having particle sizes ranging from 150 nm to 548 nm were added to fr)rm~ ticns ron~inin~ at least one UV radiation absorbing agent to determine the effectiveness of the voided latex particles in improving the absorption of UV radiation.
The voided latex particles in Examples 1 and 2 were prepared similar to the method described in U.S. Patent 4,427,836 The voided latex particles tested in Examples 1 and 2 had the following composition, unless stated otherwise:
Core: 1 pbw (60 MMA/40 MAA) Shell 1: 16 pbw (10 BMA/86 MMA/4 MAA) Shell II: 12 pbw (99.5 Sty/0.5 ALMA) Shell 111: 9 pbw (100 Sty) To swell the core, excess arnmonia (based on the tot~l equivalents of acid in the monomer) was added to the hot (80-85-C) dispersion between the polymerization of shell Il and shell III to swell the core. The voided latex particles had a final particle size and void fraction as shown in Table I.
The particle size of the voided latex particles was measured using a Brookhaven BI-90 photon correla~ion spectrometer.
The percent void fraction of the latex particles was measured by the centrifuge method described in the Detailed Description of the Invention.
21 83~22 TABLE 1: Voided Latex Particles for Examples 1 and 2 Latex Particle % Void larticles Sizt- ~nm) Fr.rt ~n 'o ymer A 5 .~o ymer B : 6 . . ) 'o ymer C .4 ' .
Po ymer D 2n. ."
.'o ymer E
'o ymer F
'o ymer G
Example 1:
A composition containing ~oided latex particles useful in the present invention was evaluated for its effectiveness in absorbing UV
radiation at varying coating thicknesses to simulate different levels of sunscreen on human skin. The composition containing the voided latex particles was also compared to a composition containing solid latex particles having a similar particle size to the voided latex particles. The following procedure was used:
Three compositions were pl epared for UV radiation absorbance measurements:
Comparative Composition A: containing no voided latex particles or solid pArticles as additives (no additives) Comparative Composition !B: containing solid polystyrene particles as an additive having a particle size of about 179 nm Composition 1: containing Polymer B as an additive (voided latex particles, see Table I) The (~omrccitinns were prepared by adding the additive at a level of 5% solids, based on total weight solids, to Hawaiian Tropic Dark Tanning Lotion with an SPF of 4, manufactured by Tanning Research Laboratories.
The UV absorbing materials in the Hawaiian Tropic Dark Tanning Lotion were 2-ethylhexyl para-methoxy~innAmA~P and menthyl anthranilate.
The compositions prepared were coated at a level of 5,10, 20 and 40 microliter per square inch (Ill/in2~ on Transpore(~) tape from Minnesota Mining and MAnllfA. tl.ring Company to simulate different levels of , . . . . ..... ....... .... . ... _ ... ... ............
~ o sunscreen on human skin. The UV radiation ~hs~rk~n~P spectra from a wavelength of 280-440 nm for eacLl sample were measured using an Optronics Laboratories 752 Spectroradiometer. The spectra at coating levels of 5,10, 20 and 40 1ll/in2 are shown in Figs. 1, 2, 3 and 4, respectively.
Composition 1 ~ nt~inin~ both at least one UV radiation absorbing agent and voided latex particles e)~hibited increased UV radiation absorbance at each coating level over the wavelengths tested (280-440 nm) as compared to the composition containing only a UV radiation absorbing agent (Comparative Composition .~). Composition 1 also exhibited increased UV radiation absorbance at each coating level as compared to Comparative composition B, containing a UV radiation absorbing agent and solid la~ex particles of a similar particle size to Polymer B. The results demonstrate that the presence of a void in the latex particles improves W
radiation absorbance of a composition containing a UV radiation absorbance agent.
Example 2:
The voided latex particles useful in the present invention were evaluated for their effectiveness ir. absorbing UV radiation at varying particle sizes in a ~mp~cjti~n containing at least one UV absorbing agent.
The procedure used was as follows:
A test composition containing the voided latex particles to be tested was prepared according to the composition shown in Table Il (Test Composition).
TABLE II: Test Com~sition Ingredient rarts b~ Weight Deionized water 75.10 Aculyn~3 22 2.25 Triethanolamine g9% 0.61 Neo Heliopan Hydro (30%) 12.00 Kathon(~) CG 0 04 Voided Latex Particles 10.00 (as solids) A control composition, hereinafter referred to as "Control," was also prepared according to the composition shown in Table II, except that no voided latex particles were added. Aculyn~19 22, supplied by Rohm and Haas Company, was added to the composition to provide thickening.
Kathon~ CG, also supplied by Rohm and ~laas Company was added to the test composition as a biocide. Neo Heliopan Hydro, a UV radiation 1 1 2 ~ 83622 absorbing agent, is supplied by Ilaarmann & Reimer and is chemically phenylben7im~ 7<)1~ sulfonic acid.
The ability of the test composition to absorb UV radiation was evaluated by measuring the sun protection factor (SPF) of the test composition. The SPF was measured using an SPF 290 Analyzer and SPF
Operating Software supplied by The Optometrics Group located in Ayer, Massachusetts. The SPF 290 Analyzer measures the UV ;~hcr~rb~nrr of a sample over UV radiation wavelengths and calculates an SPF value based on this UV absorbance spectrum. The following procedure for measuring SPF was used.
For each test composition, including the Contro~, a 10.16 cm long by 7.62 cm wide piece of Transpore(~) tape from Minnesota Mining and ~nllf;~ctllring Company was cut and placed in the SPF 290 Analyzer.
Using a 1.0 cc graduated syringe, a~.1 cc of the composition to be tested was evenly applied to a test area of about 50 square rrntimrt~r area. The composition was dried on the tape for 20 minutes.
While the composition to be tested was dryin~, a piece of tape containing no composition was measured for background UV absorbance using the SPF 290 Analyzer. The SPF 290 Ar~alyzer subtracts the background absorbance of the tape to calculate the SPF for the test composition.
After drying, the test composition was measured for SPF using the SPF 290 Analyzer in 6 different locations wi~hin the test area of the tape.
These 6 measurements were averaged together. The above procedure for measuring SPF was repeated for tlle same test composition, to obtain 6 additional SPF measurements. The 12 SPF measurements were averaged to obtain a final SPF.
TABLE III shows the Final SPF values for compositions which were tested according to the above procedure. Table III shows for each test composition, the latex particles which were tested, the particle size of the voided latex particles, the % void traction of the latex particles, and the Final SPF value. A higher SPF value for a test composition indicates that a greater amount of UV radiation is being absorbed in comparison to another test composition having a lower SPF value. The data in TABLE
III is also graphically shown in FIG. 5.
TABLE III and FIG. 5 show that the UV radiation absorbance of the test composition containing at least one UV radiation absorbing agent unexpectedly increases when the voided latex particles have a particle size of from about 100 nm to about 380 nm. The increase is especially great within the particle size range of from about 190 nm to about 350 nm.
TABLE 111: Final SPF Values for Test Compositions ~~nn~inin~
Voided Lalex Particles Composition Latex Particles Particle % Void Final Measured Tested Size Fraction SPF
(nm) Control ~one -- -- 1.3 Test c nmrncitir)n 1 'o ymer A 150 11.3 10.5 Test comrr~itinn 2 o ymer C 249 23.5 13.0 Test composition 3 'o ymer ~ 263 28.3 17.8 Test cl~mr~citinn 4 'o ymer ."" 282 28.3 14.3 Test cnnnr(-~iti--n s~i 'O ymer . ~'' 400 36.5 9.6 Test composition 6 'o ymer G 548 30.5 9.7 comparative Polymers C, D, E, F, and G were compositionAlly similar to polymer A.
RADIATION ABSORPTION OF A COMPOSITION
This is a ~ontinll~tion-in-part of application Serial No. 08/203,178 filed on February 28,1994.
FIELD OF THE INVENTION
This invention relates to a method of improving absorption of ultraviolet radiation by adding voided latex particles to a composition containing at least one ultraviole~ radiation absorbing agent.
BACKGROUND OF THE INVENTION
Six percent of the solar energy reaching the earth's surface is ultraviolet (UV) radiation having a wavelength of 290-400 nanometers (nm). This radiation has two components:
(1) 5.5/O UVA having a wavelength of 320-400 nm and (2) 0.5~1~o UVB having a wavelength of 290-320 nm.
While the UV portion of the solal~ energy is relatively small, it induces nearly 99/O of all the side effects of sunlight. UVB radiation, for example, is responsible for producing sunburn, aging and cancer of the skin. WA
radiation, for example, causes direct tanning and erythema (abnormal redness) and contributes to aging of the skin.
By avoiding exposure to sunlight, people can avoid the serious effects caused by the UV radiatior~. However, because of the nature of their work, some people cannot avoid exposure to the sun. In addition, others voluntarily expose their skin to the sun to tan, sometimes to extremes. Therefore, protection against the harmful effects of the sun is important.
Protection from these harmful effects of UV radiation exposure is available in the form of both topically applied formulations containing at least one physical blocker, or at least one chemical absorber, or combinations thereof. Physical blockers include active ingredients such as red petrolatum, titanium dioxide and zinc oxide. Chemical absorbers include active ingredients, such as p~ra-aminobenzoic acid (more commonly known as PABA), which are generally transparent when applied and act by absorbing UV radiation, offering selective protection against certain UV wave bands, d!epending upon the absorption spectrum of the particular active ingredient incorporated into the formulation.
The effectiveness of a sunscreen formulation is generally assessed by how well it protects the skin in terms of a Sun Protection Factor (SPF) which is defined as the ratio of the amount of energy required to produce a minimal erythema on sunscreen protected skin to the amount of energy required to produce the same level of erythema on unprotected skin.
A number of the chemical absorbers and physical blockers, herein after referred to as "UV radiation absorbing agents," typically used in sunscreen formulations have adverse toxicological effects. Therefore, it is desirable to reduce the level of U~ radiation absorbing agents present in a sunscreen formulation without reducing the level of plolt-lio,~.
One attempt to reduce the level of UV radiation absorbing agents in a sunscreen formulation is disclosed in U.S. Patent Number 4,804,531 to Grollier, hereinafter referred to as "Grollier." Grollier discloses adding to a cosmetic screening rrlmrrSi~iOn an aqueous ~licrrr~i~)n of water insoluble polymer particles where the polynller particles comprise a) an ionic polymer forming a core capable of being swollen, and b) a polymer forming a sheath at least partially encapsulating the core. The water insoluble polymer particles are disclosed to be film forming, to have a sheath glass transition temperature below 50 C, and to have an average particle size before swelling of from 70 nanometers (nm) to 4500 nm.
Grollier discloses that when the water insoluble polymer particles are added to a cosmetic screening composition at a level of from 0.1 to 10 weight percent, based on the total weight of the cosmetic screening composition, the absorption of U~ radiation in the cosmetic screening composition is increased.
Improving upon the teachings of Grollier, we have unexpectedly found that voided latex particles having certain particle sizes, increase the absorbance of UV radiation in a composition containing one or more UV
radiation absorbing agents.
SUMMARY O~F THE INVENTION
We have discovered a method for improving UV radiation absorption of a composition, comprising: adding to said composition from about 0.1 weight percent to about 50 weight percent of latex particles, based on total weight of nonvolatiles, wherein the composition comprises at least one UV radiation absorbing algent, and wherein the latex particles contain a void and have a particle size of from about 100 nm to about 380 nm .
BRIEF DESCRlrTrON OF Tr~E DRAWINGS
rn the drawings:
FIG. 1 is a UV radiation absorbance spectrum from a wavelength of 280-440 nm for compositions contAining no additives, solid latex particles and Yoided latex particles at a coating level of 5 microliters per square inch (Ill/in2). The active ingredients in the compositions are 2-ethylhexyl para-methoxycinnamate and menthyl alnthranilate. The additiYes are incorporated at a level of 5/O by weight, based on total weight nonvolatiles.
FIG. 2 is a UV radiation absorbance spectrum from a wavelength of 280-440 nm for compositions containing no additives and voided latex particles at a coating level of 10 111/in2. The active ingredients in the compositions are 2-ethylhexyl para-methoxycinnamate and menthyl anthranilate. The additives are incorporated at a level of 5/O by weight, based on total weight nonvolatiles.
FIG. 3 is a UV radiation absorbance spectrum from a wavelength of 280-440 nm for compositions t -)n~Ainin~ no additives, solid latex particles and voided latex particles at a coating level of 20 111/in2. The active ingredients in the compositions ale 2-ethylhexyl para-methoxyl-innAm~P
and menthyl anthranilate. The additives are incorporated at a level of 5%
by weight, based on total weight n.onvolatiles.
FIG. 4 is a UV radiation absorbance spectrum from a wavelength of 280-440 nm for compositions cont~ining no additives, solid latex particles and voided latex particles at a coating level of 40 ~LI/in2. The active ingredients in the compositions are 2-ethyl~exyl para-methoxycinnamate and menthyl anthranilate. The additives are incorporated at a level of 5%
by weight, based on total weight n.onvolatiles.
FIG. 5 is a graph showing falr 6 UV radiation absorbing compositions, the r~lA~ir nchip of the Sun Protection Factor (SPF) for the compositions (Y axis) versus the particle size, in nm, of voided latex particles contained in the composi~:ions (X axis). The voided latex particles (as solids) are incorporated in the compositions at a level of 10 weight percent, based on total weight non.volatiles. In addition to the voided latex particles, the compositions also contained, phenylben7imi(1A~n'^
sulfonic acid, a UV radiation absorbing agent.
` 4 21 83~
DETAILED DESCRI;PTION OF THE INVE~TION
The method of the invention improves the UV radiation absorption of a composition containing at least one UV radiation absorbing agent. The method of the present invention includes incorporating from about 0.1 weight percent to about 50 weight percent, and preferably from about 1 weiglllt percent to about 20 weight percent, based on total weight nonvolatiles, of voided latex particles to a composition containing at least one ultraviolet radiation absorbing agent.
As used herein, the term "UV radiation" includes both UVA and UVi3 radia tion.
The latex particles useful in the method of this invention have a particle size of from about 100 namometers (nm) to about 380 nm, preferably from about 150 nm to ~Ibout 375 nm, more preferably from about 190 nm to about 350 nm, and most preferably from about 251 nm to about 325 nm as measured by a Brookhaven Bl-90 photon correlation spectrometer.
For a given particle size, it is desirable to produce latex particles with a m~imllm void fraction as current processing techniques and particle integrity will permit. Preferably, l:he latex particles contain a void with a void fraction of from about 0.1% to about 50%, and more preferably from about 5% to about 50%. The void fractions are rlrt~rminrd by romrarinr the volume occupied by the latex particles after they have been rrlmr~rt,o~l from a dilute dispersion in a centrifuge to the volume of non-voided particles of the same composition.
The voided latex particles useful in the method of this invention are formed from a multistaged pa~ticle comprising at least one core polymer and at least one shell polymer. The core polymer and shell polymer may be made in a single polymerization step or in a sequence of polymerization steps.
The voided latex particles are prepared by conventional polymerization techniques such as, sequential emulsion polymerization, including those processes disclosed in U.S. Patents 4,427,836; 4,469,825;
4,594,363; 4,677,003; 4,920,160; 4,970,241, whose disclosures are incorporated herein by reference. The voided latex particles may also be prepared, for example, by polymerization techn~ques disc~osed in European Patent Application 0,267,726, European Patent Application 0,331,421, U.S. Patent 4,910,229, or U.S. Patent 5,157,084.
~, . 2 ~ 83622 The monomers used in the emulsion polymerization of the shell polymer of the voided latex particles preferably comprise one or more non-ionic ethylenically unsaturated monomer. Optionally, one or more monoethylenically unsaturated monomers containihg at least one carboxylic acid group may be polymerized in the shell.
The m~lnr~mPr.c which comprise the shell are selected to provide a glass transition temperature (Tg) in at least one shell which is high enough to s~lpport the void withitl the latex particle. Preferably the Tg of at least one shell is greater than 50 C, more preferably greater than 60 C, and most preferably greater than ~0 C as measured by differential scanning calorimetry.
The mt~nflmPrs used in the emulsion polymerization of the core polymer of the voided latex particles preferably comprise one or more monoethylenically unsaturated monomers containing at least one carboxylic acid group. Preferably, the core comprises at least 5 weight percent of the monoethylenically unsaturated monomers containing at least one carboxylic acid, based on total monomer weight of the core. The core polymer may be obtained, for example, by the emulsion homopolymerization of the monoethylenically unsaturated monomer containing at least one carboxylic acid group or by copolymerization of two or more of the monoethylenically unsaturated monomers containing at least one carboxylic acid group. Preferably, the monoethylenically unsaturated monomer containin~ at least one carboxylic acid group is copolymerized with one or more non-ionic ~that is, haYing no ionizable group) ethylenically unsaturated monomers.
The core polymer or shell polymer may optionally contain from about 0.1 weight percent to about ~0 weight percent, preferably about 0.1 weight percent to about 3 weight percent, based on the total monomer weight of tile core, of polyethylen;cally unsaturated monomer, such as ethylene glycol di(meth)acrylate, allyl (meth)acrylate, 1,3-butanediol di(meth)acrylate, diethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, or divinylbenzene. Alternatively, the core polymer or shell polymer may optionally contain from about 0.1 weight percent to about 60 weight percent, based on the total monomer weight of the core, of butadiene.
Suitable monoethylenically unsaturated monomers containing at least one carboxylic acid group include for example acrylic acid and methacrylic acid, acryloxypropionic acid, (meth)acryloxypropionic acid, 6 2t83622 itaconic acid, aconitic acid, maleic acid or anhydride, fumaric acid, crotonic acid, monomethyl maleate, monomethyl fumarate, and monomethyl itaconate. Acrylic acid and methacrylic acid are preferred.
Suitable non-ionic ethylenically unsaturated monomers include for example styrene, vinyltoluene, ethylene, vinyl acetate, vinyl chloride, vinylidene chloride, acrylonitrile, (meth)acrylamide, (C1-C20) alkyl or (C3-C20) alkenyl esters of (meth)acrylic acid, such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, benzyl (meth)acrylate, lauryl (meth)acrylate, oleyl (meth)acrylate, palmityl (meth)acrylate and stearyl (meth)acrylate. As used herein, the term "(meth)acrylic" is intended to serve as a generic expression embracing both acrylic and methacrylic.
The void of the latex particles is preferably produced by swelling the core with a swelling agent ~ in~ one or more volatile components.
The swelling agent permeates the shell to swell the core. The volatile components of the swelling agent can then be removed by drying the latex particles, causing a void to be fornled within the latex particles. Preferably, the swelling agent is an aqueous base. The aqueous base useful for swelling the core includes, for example, ammonia, ammr1nil'm hydroxide, alkali metal hydroxides, such as sodium hydroxide, or a volatile amine such as trimethylamine or trieth~lamine.
The voided latex particles may be added to the composition with the swelling agent present in the core When the latex particles are added to the composition with the swelling agent present in the core, the volatile components of the swelling agent will be removed upon drying of the composition. The voided latex pal-ticles may also be added to the composition after removing the volatile components of the swelling agent.
In addition to the voided la,tex particles, the composition improved by the method of the present inYention contains at least one UV radiation absorbing agent. The UV radiation absorbing agent may be incorporated into the composition at a level to produce a desired sun protection factor.
For example, the UV radiation abs~rbing agent may be added to the composition at a level of generally from about 0.1 weight percent to about 15 weight percent, based on the total weight of nonvolatiles in the composition.
The UV absorbing agents used in the method of this invention are conventional materials. Suitable UV radiation absorbing agents include, 21 836~2 for example, oxybenzone, dioxybenzone, sulisobenzone, menthyl anthranilate, para-aminobenzoic acid, amyl para-dimethyl~minot!Pn7o:-acid, octyl para-dimethylaminobenzoate, ethyl 4-bis (hydroxypropyl) para-aminobénzoate, polyethylene glycl~l (PEG-25) para-aminobenzoate, ethyl 4-bis (hydroxypropyl) aminobenzoate, rliPth~nnl~mine para-methyoxycinnamate, 2-ethoxyeth~l para-methoxycinnamate, ethylhexyl para-methoxyrinn~n~ ~P, octyl paramethoxyninn~m~P, isoamyl para-methoxycinnamate, 2-ethylhexyl 2-cyano-3,3-diphenyl-acrylate, 2-ethylhexyl salicylate, hnmomPn~h~l salicylate, glyceryl aminobenzoate, triethanolamine salicylate, digalloyl trioleate, lawsone with dihydroxyacetone, 2-phenylbenzin~idazole-5-sulfonic acid, benzylidine camphor, avobenzone, titanium dioxide, and zinc oxicle.
The composition improved by the method of this invention may also include other conventional ingredients used in UV absorbing compositions. For example, if the composition is used as a sunscreen, it may additionally include water, film forming materials, PmlllcifiPr~, water, ~molliPn~c, waterproofing agents, oils, stabilizers, thickeners, preservatives, perfume, colorants, insPr~ lPc, or humectants or combinations thereof. If the composition is used as a cosmetic, it may additionally include, for example, water, film forming materials, emulsifiers, softeners, emollients, ,:)ils, stabilizers, thickeners, preservatives, perfume, colorants, or pigments, or combinations thereof.
The composition improved by the method of this invention may be used in any application where protection from UV radiation is useful. For example, the improved composition may be used on human skin and hair, such as, for example personal care products, including, cosmetics, sunscreens, and hair care products. In addition, the method of this invention is also useful in improving the UV absorption and protection for coatings on plant life, plastics, ~ood, for example in the form of a clear varnish.
The method of this invention may be used to improve the UV
radiation absorption in either clear or pigmented formulations The method is particularly useful if a c~ear formulation is desired, such as a sunscreen forml~ n, because the addition of the voided latex particles having a particle size of less than about 300 nm does not significantly contribute to whiteness.
The method of this invention enables formulators to either increase the UV radiation absorbance of a given formulation or reduce the 8 21836~2 level of the UV radiation absorbinlg agent present in the form~ n while maintaining a given UV radiation absorbance.
The compositions improved by the method of this invention may be applied to the skin at coating volumes, for example, of from about 0.5 microliters per square centimeter to about 4 microliters per square cpntimetpr~
EXAMPLES
Some embodiments of the invention will now be described in detail in the following examples. The following abbreviations are used in the Examples:
MMA weight E~ercent methyl methacrylate BMA weight percent butyl methacrylate MAA weight percent methacrylic acid Sty weight F~ercent styrene ALMA weight percent allyl methacrylate pbw parts by weight For Examples 1 and 2, voidc~d latex particles having particle sizes ranging from 150 nm to 548 nm were added to fr)rm~ ticns ron~inin~ at least one UV radiation absorbing agent to determine the effectiveness of the voided latex particles in improving the absorption of UV radiation.
The voided latex particles in Examples 1 and 2 were prepared similar to the method described in U.S. Patent 4,427,836 The voided latex particles tested in Examples 1 and 2 had the following composition, unless stated otherwise:
Core: 1 pbw (60 MMA/40 MAA) Shell 1: 16 pbw (10 BMA/86 MMA/4 MAA) Shell II: 12 pbw (99.5 Sty/0.5 ALMA) Shell 111: 9 pbw (100 Sty) To swell the core, excess arnmonia (based on the tot~l equivalents of acid in the monomer) was added to the hot (80-85-C) dispersion between the polymerization of shell Il and shell III to swell the core. The voided latex particles had a final particle size and void fraction as shown in Table I.
The particle size of the voided latex particles was measured using a Brookhaven BI-90 photon correla~ion spectrometer.
The percent void fraction of the latex particles was measured by the centrifuge method described in the Detailed Description of the Invention.
21 83~22 TABLE 1: Voided Latex Particles for Examples 1 and 2 Latex Particle % Void larticles Sizt- ~nm) Fr.rt ~n 'o ymer A 5 .~o ymer B : 6 . . ) 'o ymer C .4 ' .
Po ymer D 2n. ."
.'o ymer E
'o ymer F
'o ymer G
Example 1:
A composition containing ~oided latex particles useful in the present invention was evaluated for its effectiveness in absorbing UV
radiation at varying coating thicknesses to simulate different levels of sunscreen on human skin. The composition containing the voided latex particles was also compared to a composition containing solid latex particles having a similar particle size to the voided latex particles. The following procedure was used:
Three compositions were pl epared for UV radiation absorbance measurements:
Comparative Composition A: containing no voided latex particles or solid pArticles as additives (no additives) Comparative Composition !B: containing solid polystyrene particles as an additive having a particle size of about 179 nm Composition 1: containing Polymer B as an additive (voided latex particles, see Table I) The (~omrccitinns were prepared by adding the additive at a level of 5% solids, based on total weight solids, to Hawaiian Tropic Dark Tanning Lotion with an SPF of 4, manufactured by Tanning Research Laboratories.
The UV absorbing materials in the Hawaiian Tropic Dark Tanning Lotion were 2-ethylhexyl para-methoxy~innAmA~P and menthyl anthranilate.
The compositions prepared were coated at a level of 5,10, 20 and 40 microliter per square inch (Ill/in2~ on Transpore(~) tape from Minnesota Mining and MAnllfA. tl.ring Company to simulate different levels of , . . . . ..... ....... .... . ... _ ... ... ............
~ o sunscreen on human skin. The UV radiation ~hs~rk~n~P spectra from a wavelength of 280-440 nm for eacLl sample were measured using an Optronics Laboratories 752 Spectroradiometer. The spectra at coating levels of 5,10, 20 and 40 1ll/in2 are shown in Figs. 1, 2, 3 and 4, respectively.
Composition 1 ~ nt~inin~ both at least one UV radiation absorbing agent and voided latex particles e)~hibited increased UV radiation absorbance at each coating level over the wavelengths tested (280-440 nm) as compared to the composition containing only a UV radiation absorbing agent (Comparative Composition .~). Composition 1 also exhibited increased UV radiation absorbance at each coating level as compared to Comparative composition B, containing a UV radiation absorbing agent and solid la~ex particles of a similar particle size to Polymer B. The results demonstrate that the presence of a void in the latex particles improves W
radiation absorbance of a composition containing a UV radiation absorbance agent.
Example 2:
The voided latex particles useful in the present invention were evaluated for their effectiveness ir. absorbing UV radiation at varying particle sizes in a ~mp~cjti~n containing at least one UV absorbing agent.
The procedure used was as follows:
A test composition containing the voided latex particles to be tested was prepared according to the composition shown in Table Il (Test Composition).
TABLE II: Test Com~sition Ingredient rarts b~ Weight Deionized water 75.10 Aculyn~3 22 2.25 Triethanolamine g9% 0.61 Neo Heliopan Hydro (30%) 12.00 Kathon(~) CG 0 04 Voided Latex Particles 10.00 (as solids) A control composition, hereinafter referred to as "Control," was also prepared according to the composition shown in Table II, except that no voided latex particles were added. Aculyn~19 22, supplied by Rohm and Haas Company, was added to the composition to provide thickening.
Kathon~ CG, also supplied by Rohm and ~laas Company was added to the test composition as a biocide. Neo Heliopan Hydro, a UV radiation 1 1 2 ~ 83622 absorbing agent, is supplied by Ilaarmann & Reimer and is chemically phenylben7im~ 7<)1~ sulfonic acid.
The ability of the test composition to absorb UV radiation was evaluated by measuring the sun protection factor (SPF) of the test composition. The SPF was measured using an SPF 290 Analyzer and SPF
Operating Software supplied by The Optometrics Group located in Ayer, Massachusetts. The SPF 290 Analyzer measures the UV ;~hcr~rb~nrr of a sample over UV radiation wavelengths and calculates an SPF value based on this UV absorbance spectrum. The following procedure for measuring SPF was used.
For each test composition, including the Contro~, a 10.16 cm long by 7.62 cm wide piece of Transpore(~) tape from Minnesota Mining and ~nllf;~ctllring Company was cut and placed in the SPF 290 Analyzer.
Using a 1.0 cc graduated syringe, a~.1 cc of the composition to be tested was evenly applied to a test area of about 50 square rrntimrt~r area. The composition was dried on the tape for 20 minutes.
While the composition to be tested was dryin~, a piece of tape containing no composition was measured for background UV absorbance using the SPF 290 Analyzer. The SPF 290 Ar~alyzer subtracts the background absorbance of the tape to calculate the SPF for the test composition.
After drying, the test composition was measured for SPF using the SPF 290 Analyzer in 6 different locations wi~hin the test area of the tape.
These 6 measurements were averaged together. The above procedure for measuring SPF was repeated for tlle same test composition, to obtain 6 additional SPF measurements. The 12 SPF measurements were averaged to obtain a final SPF.
TABLE III shows the Final SPF values for compositions which were tested according to the above procedure. Table III shows for each test composition, the latex particles which were tested, the particle size of the voided latex particles, the % void traction of the latex particles, and the Final SPF value. A higher SPF value for a test composition indicates that a greater amount of UV radiation is being absorbed in comparison to another test composition having a lower SPF value. The data in TABLE
III is also graphically shown in FIG. 5.
TABLE III and FIG. 5 show that the UV radiation absorbance of the test composition containing at least one UV radiation absorbing agent unexpectedly increases when the voided latex particles have a particle size of from about 100 nm to about 380 nm. The increase is especially great within the particle size range of from about 190 nm to about 350 nm.
TABLE 111: Final SPF Values for Test Compositions ~~nn~inin~
Voided Lalex Particles Composition Latex Particles Particle % Void Final Measured Tested Size Fraction SPF
(nm) Control ~one -- -- 1.3 Test c nmrncitir)n 1 'o ymer A 150 11.3 10.5 Test comrr~itinn 2 o ymer C 249 23.5 13.0 Test composition 3 'o ymer ~ 263 28.3 17.8 Test cl~mr~citinn 4 'o ymer ."" 282 28.3 14.3 Test cnnnr(-~iti--n s~i 'O ymer . ~'' 400 36.5 9.6 Test composition 6 'o ymer G 548 30.5 9.7 comparative Polymers C, D, E, F, and G were compositionAlly similar to polymer A.
Claims (7)
1. A method for improving UV radiation absorption of a composition, comprising: adding to said composition from about 0.1 weight percent to about 50 weight percent of latex particles, based on total weight nonvolatiles, wherein the composition comprises at least one UV
radiation absorbing agent, and wherein the latex partides contain a void and have a particle size of from about 100 nm to about 380 nm.
radiation absorbing agent, and wherein the latex partides contain a void and have a particle size of from about 100 nm to about 380 nm.
2. The method of claim 1, wherein the latex particles are added to said composition to provide a level from about 1.0 weight percent to about 20 weight percent of the latex particles in said composition.
3. The method of claim 1, wherein the particle size of the latex particles is from about 150 nm to about 375 nm.
4. The method of claim 1, wherein the particle size of the latex particles is from about 190 nm to about 350 nm.
5. The method of claim 1 wherein the latex particles have a void fraction of from about 0.1% to about 50%.
6. The method of claim 1 wherein the latex particles have a void fraction of from about 5% to about 50%.
7. The method of claim 1 wherein the UV radiation absorbing agent is a chemical selected from the group consisting of oxybenzone, dioxybenzone, sulisobenzone, menthyl anthranilate, para-aminobenzoic acid, amyl para-dimethylaminobenzoic acid, octyl para-dimethylaminobenzoate, ethyl 4-bis (hydroxypropyl) para-aminobenzoate, polyethylene glycol (PEG-25) para aminobenzoate, ethyl 4-bis (hydroxypropyl) aminobenzoate, diethanolamine para-methyoxycinnamate, 2-ethoxyethyl para-methoxycinnamate, ethylhexyl para-methoxycinnamate, octyl paramethoxycinnamate, isoamyl para-methoxycinnamate, 2-ethylhexyl 2-cyano-3,3-diphenyl-acrylate, 2-ethylhexyl salicylate, homomenthyl salicylate, glyceryl aminobenzoate, triethanolamine salicylate, digalloyl trioleate, lawsone with dihydroxyacetone, 2-phenylbenzimidazole-5-sulfonic acid, benzylidine camphor, avobenzone, titanium dioxide and zinc oxide.
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|---|---|---|---|
| US08/518,698 | 1995-08-24 | ||
| US08/518,698 US5663213A (en) | 1994-02-28 | 1995-08-24 | Method of improving ultraviolet radiation absorption of a composition |
Publications (1)
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|---|---|
| CA2183622A1 true CA2183622A1 (en) | 1997-02-25 |
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|---|---|---|---|
| CA002183622A Abandoned CA2183622A1 (en) | 1995-08-24 | 1996-08-19 | Method of improving ultraviolet radiation absorption of a composition |
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| US (1) | US5663213A (en) |
| EP (1) | EP0761201B1 (en) |
| JP (1) | JP3827776B2 (en) |
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| DE (1) | DE69618400T2 (en) |
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-
1995
- 1995-08-24 US US08/518,698 patent/US5663213A/en not_active Expired - Lifetime
-
1996
- 1996-08-12 AR ARP960103961A patent/AR003249A1/en unknown
- 1996-08-19 CA CA002183622A patent/CA2183622A1/en not_active Abandoned
- 1996-08-19 DE DE69618400T patent/DE69618400T2/en not_active Expired - Lifetime
- 1996-08-19 EP EP96306032A patent/EP0761201B1/en not_active Expired - Lifetime
- 1996-08-21 ZA ZA967102A patent/ZA967102B/en unknown
- 1996-08-22 MX MX9603589A patent/MX9603589A/en unknown
- 1996-08-22 BR BRPI9603514-5A patent/BR9603514B1/en not_active IP Right Cessation
- 1996-08-22 AU AU64216/96A patent/AU714730B2/en not_active Expired
- 1996-08-23 CN CNB961114991A patent/CN1138522C/en not_active Expired - Lifetime
- 1996-08-23 JP JP24116796A patent/JP3827776B2/en not_active Expired - Lifetime
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| DE69618400T2 (en) | 2002-08-14 |
| EP0761201A1 (en) | 1997-03-12 |
| AU714730B2 (en) | 2000-01-06 |
| BR9603514B1 (en) | 2009-01-13 |
| MX9603589A (en) | 1997-06-28 |
| JPH09104822A (en) | 1997-04-22 |
| AU6421696A (en) | 1997-02-27 |
| AR003249A1 (en) | 1998-07-08 |
| DE69618400D1 (en) | 2002-02-14 |
| JP3827776B2 (en) | 2006-09-27 |
| CN1138522C (en) | 2004-02-18 |
| BR9603514A (en) | 1998-05-12 |
| ZA967102B (en) | 1997-03-05 |
| EP0761201B1 (en) | 2002-01-09 |
| CN1148955A (en) | 1997-05-07 |
| US5663213A (en) | 1997-09-02 |
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| FZDE | Discontinued |
Effective date: 20030819 |