TW201014610A - Compositions comprising an ultraviolet radiation-absorbing polymer - Google Patents

Abstract

Ultraviolet radiation-absorbing polymers having a first pendant group that comprises an ultraviolet radiation-absorbing moiety and a second pendant group that comprises at least one siloxane linkage and/or an intermediate length carbon chain are disclosed. Personal care compositions including the ultraviolet radiation-absorbing polymer are provided.

Description

201014610 VI. INSTRUCTIONS OF THE INVENTION: FIELD OF THE INVENTION The present invention relates to an improved sunscreen compound and a topically acceptable composition comprising such sunscreen compounds. [Prior Art] Prolonged exposure to uv radiation (eg, from sunlight) can cause photodermatosis 13 and erythema formation and increase the risk of skin cancer (eg, melanoma and accelerated skin aging (eg loss of skin elasticity and wrinkles). The compounds are commercially available to protect the body from the diverse effects of ultraviolet light. For example, various sunscreen compounds can absorb or block the ultraviolet spectrum of different portions of the ultraviolet, such as having a wavelength in the UV-Α range (about 320 to 400 nm) and UV. - UV light of both ranges (about 280 to about 320 nm), or some combination of these spectral ranges. It has been suggested to use sunscreen molecules with high molecular weight in order to reduce the penetration of sunscreen molecules into the epidermis. There are only a limited number of options for high molecular weight sunscreen compounds. Accordingly, Applicants have recognized that it is desirable to have novel polymeric sunscreen compounds suitable for inclusion in topical sunscreen compositions (polymerization that absorbs ultraviolet radiation) Also want a polymer that absorbs eUV, when formulated, provides one or more good Composition of cloth, low gloss, non-greasy texture, water repellency, high SPF, high PFA, and suitable PFA/SPF ratio (broad spectrum protection). Applicants have discovered that a uv-absorbing polymer is used alone or in combination with others. The uv-absorbing polymer blend provides a particular advantage. The UV-absorbing polymer comprises a first suspension group comprising a UV absorbing portion 3 201014610 parts and a second comprising at least one oxymethane linkage and/or a medium length carbon bond. Suspension base. SUMMARY OF THE INVENTION In one aspect, the invention features a uv-absorbing polymer having the following chemical structure: R· R· I - UH2 - ^ C · IH2 ijT - C^r〇1 0 1 I 0 I 1 R1 n I r2 ❹ where Ri is the first suspension group including the portion that absorbs UV', for example, the absorption UV-A P knife is preferably a UV-absorbing triplet; R2 is the second suspension base including: a) to the previous (eg, from 1 to about 50) a siloxane coupling 'b) a saturated or unsaturated hydrocarbon moiety having a median number of carbon atoms (eg, 7 to 16 carbon atoms), or a combination thereof; each R, independently Η or ( ^ to C12 alkyl; n is i to 6000 'm is 2 to 6300. In a concrete , The UV-absorbing polymeric ❿ having weight average molecular weight of at least about 2000 and comprising at least about 5 mole%

Rl. In another specific example, 'R2 has no UV-absorbing portion. The invention has the following features: an aqueous composition comprising water and a UV-absorbing polymer having the following structure: ch2—C- "CH;"C" 201014610 A R1 is the first suspension base The portion that absorbs UV, such as a portion that absorbs UV-A, is preferably a UV-absorbing triazole; and R2 is a second pendant group comprising: a) at least one (eg, from 1 to about 50) decane linkage, b) a saturated or unsaturated hydrocarbon moiety having a medium number of carbon atoms (eg, 7 to 16 carbon atoms), or c) a combination thereof; each R' is independently η or Q to C12 alkyl; η is from 1 to 6000; m is 2 To 6300. In one embodiment, the UV absorbing polymer has a weight average molecular weight of at least about 2 Torr and includes at least about 5 mole % ❹ Ri. In another embodiment, R2 has no UV-absorbing portion. In another aspect, the invention relates to a method of protecting mammalian skin or hair from UV radiation, comprising locally applying a uv-absorbing polymer of the invention to the skin or hair. In another aspect, the invention features a composition comprising a first UV absorbing polymer comprising a UV-A absorbing portion and a second UV absorbing polymer comprising a UV absorbing portion. The blend is capable of providing both synergistic SPF and synergistic PFA protection over a range of mass percentages of the two polymers of at least about 〇鄕°. In another aspect, the invention features a composition comprising an absorption UV-A a portion of the first UV absorbing polymer and a second UV absorbing polymer comprising a UV absorbing portion, wherein the first UV absorbing polymer has a PFA/SPF ratio greater than 0.3 and the second UV absorbing polymer has a PFA The /SPF ratio is less than 0.3. In another aspect, the invention features a composition comprising: 1) a first UV absorbing polymer having a carbon chain (c-C) backbone and comprising an absorbing UV-A moiety, and 2) a second absorption A UV polymer with a oxoxane bone 5 201014610 dry and containing a UV-B absorbing portion.

The towel (4) is a composition comprising: ^ Chu 'with a C-C backbone, comprising a first absorption UV A eF: S silver-suspension base and a second suspension soil comprising at least one siloxane alkyl group - a portion of the suspension base that does not absorb the rim, and 2) a second UV absorbing poly sigma 'containing at least one portion of the cerium oxide and the second absorbing uv. It is believed that the skilled artisan will be able to devise the invention to its fullest extent. The following specific examples are to be construed as illustrative only and not in any way limiting the remaining disclosure. Unless otherwise defined, all technical and scientific terms used herein have the same meaning meaning Moreover, all publications, patent applications, patents, and other references mentioned herein are incorporated by reference. As used herein, unless otherwise specified, all of the alkyl, alkenyl, and alkoxy groups may be straight, cyclic, or branched. As used herein, unless otherwise indicated, the term "molecular weight" refers to the weight average molecular weight (Mw). The term "mass ratio" as used herein refers to the ratio of the mass percentage of the first component to the mass percentage of the second component, such as two UV-absorbing polymers, two monomers for mutual reaction in the polymerization reaction, or Two repeating units present in the polymer after polymerization. The mass ratio can be expressed as a percentage ratio or a "rate format" (eg 9: 1) added to 100% (eg 90%/10%). UV absorbing polymer A specific example of the invention relates to a composition comprising a polymer that absorbs ultraviolet radiation (i.e., a polymer that absorbs UV). "UV-absorbing polymer" 201014610 means that the polymer absorbs radiation in several portions of the ultraviolet spectrum (290 nm to 400 nm) and preferably has an extinction coefficient of at least about 1000 knknT1 for at least one wavelength in the ultraviolet spectrum defined above, for example greater than 1〇, 〇〇〇 or 100,000 or lOOO'OOOmofcm-1. In a preferred embodiment, the UV absorbing polymer has a chemical structure: - (A) η - (Β) The UV absorbing polymer typically comprises η molar first repeating unit, A; and m mor second repeating unit , B. Thus, the uv radiation-absorbing polymer of the present invention is a copolymer having at least two repeating units. The polymer typically comprises a backbone of carbon atoms (e.g., carbon chains or C-C backbones) attached to the covalently bonded pendant groups. Those skilled in the art will recognize that "backbone" generally refers to a portion of a covalent bond in a polymer. If more than one of the parts is present, the bones of the bones and the polymer of the conjugated atoms are divided into smaller groups of the atoms of the atoms. The structure of the υ 构 表示 ’ ’ ’ ’ ’ ’ υ 的 的 的 的 的 可以 可以 可以 可以

Rf -CH, c R, Μ c=o 1 Ϊ c=o I 0 I 0 1 1 Ri n 1 «2 In this specific example, 笙.^ Am (, ίλ, as_ first repetition is usually included The first suspension 201014610, which is bonded to the C-C backbone via, for example, a bonding group, is about 7000 2 dry, usually consisting of about 7 carbon atoms, preferably about 7 to about 7. Preferably, from about 10 to about 5 carbon atoms, even more preferably from about 4 to about one carbon atom, even more preferably from about to about one carbon atom. The first suspension base (Rl) contains 苐-absorbing uv (also referred to herein as absorbing uv chromophore), J Zanba 丞 "UV chromophore", or simply "hair base"). The first portion that absorbs UV absorbs in the ultraviolet spectrum. Ο In the case of particularly good real money, the part of the first-record UV is the part that absorbs UV-A. The "portion of the absorbing pulse" means that the ultraviolet spectrum of the uv_A portion (32 〇 nm to 4 〇〇 nm) has a considerable appreciable absorbance. For example, when the compound containing the chemical component is destroyed, the molar extinction coefficient measured for at least one wavelength in this wavelength range may yield at least about 100 mol ^ mi ' preferably at least about, more preferably at least about 4000 m. 〇l into γΐ. In a preferred embodiment, the molar extinction coefficient of at least 4% of the wavelength of the partial spectrum is at least about iOOOmd-icm·!. Examples of the moiety that absorbs UV-A include triazoles such as benzotriazole; camphors such as benzylidene camphor and its derivatives (for example, available from [, (3) 丨, also known as ECAMSULE or Mexoryisx. Dicamphorsulfonic acid); dibenzyl decyl decane and its derivatives. In a particularly preferred embodiment, the portion that absorbs uv is a UV-absorbing triazole and/or a UV-absorbing benzhydrazine group. In a further preferred embodiment, in order to provide both light stability and strong UV-A absorbance, the UV-absorbing portion is a UV-absorbing triazole. "UV-absorbing triazole" means that the portion of the absorption contains a five-membered heterocyclic ring having two carbons 8 201014610 atoms and three nitrogen atoms, such as a compound of formula I or II: (I). Examples of UV-absorbing triazoles

Wherein each R!4 is independently selected from the group consisting of hydrogen, q-CM alkyl, alkoxy, fluorenyl, alkyloxy, alkylamine, and halogen; each Ri5 and R22 are independently selected. a group consisting of hydrogen, CrC2 (alkyl), alkoxy, decyl, alkyloxy, and alkylamino, at least one of r15 and r22 is not hydrogen; r2i is selected from alkyl, alkoxy A group, a decyl group, an alkyloxy group, and an alkylamine group. The 'Rl5 or R21 group in Formula 1 can be oriented to directly bond to the (ester) linkage linking the UV-absorbing triazole to the c-C backbone. In Formula II, R15 and R22 can be oriented for direct bonding to a triazole that is attached to absorb u V and a dry (ester) linkage of C-C bone 9 201014610. Monomeric Compounds Formulas I and II are described in USP 5,869,030 and include, but are not limited to, fluorenylene bis-benzotriazolyl tetramethyl butyl phenol (TINSORB®, Ciba Specialty Chemicals Corporation, Greensboro, North Carolina, United States). The other monomeric UV-absorbing dibenzyl decyl decane comprises 2-(4-diethylamino-2-hydroxybenzyl)-benzylic acid hexyl ester, commercially available as UVINUL A Plus, from Parsippany, New Jersey. BASF of Western State. In a preferred embodiment, the UV-absorbing triazole is a compound of formula I wherein Rm is halogen (preferably gas), R15 is butyl and R21 is -CH2CH2C〇2C8H17 (which can be converted to an acidic form and subsequently converted It is in an ethylenically unsaturated form to make it suitable for polymerization). The UV-absorbing triazole can be obtained as an octyl-3-[3-tert-butyl-4-trans-5-(5-chloro-2H-benzotris-β-yl-2-phenyl)phenyl group of TINUVIN 109. Propionic acid vinegar and its isomer, 2-ethylhexyl-3-[3-t-butyl-4-trans-5-(5-aero-2-indole-benzotriazin-2-yl)phenyl a blend of propionate esters from Ciba Inc. (BASF Corporation). Another suitable example of a UV-absorbing triazole is 2-[3,-t-butyl-5'-(2-decyloxycarbonylethyl)-2,-hydroxyphenyl]-2H-benzotriazole The transesterified product with polyethylene glycol 300 is also commercially available as TINUVIN 213, also from Ciba Inc. The UV-absorbing dibenzylhydrazine methane can be represented by the formula in the formula R19) m9 - 20 m10 (III) 201014610 wherein R19 and R2 are independently CVQ alkyl or (^-(:8 alkoxy, m9 is 0) Up to 3, mlO is from 1 to 3. R19 and R2〇 can be oriented to bond directly to the UV-bonded dibenzyl aryl ketone and C-C backbone (ester) linkage. Examples and syntheses of methicone compound compositions are described in USP 4,489,057 'and include, but are not limited to, 4-(1,1-dimethylethyl)-4'-methoxy bis- aryl ketone (Asia Av〇benzone and sold under 〇PARSOL 1789, Roche Vitamins and Fine Chemicals, Nutley 'New Jersey' USA, 2-mercaptodibenzyl decane, 4 曱 benzyl dibenzyl hydrazine Kei, 4-isopropyldibenzylhydrazine, 4-tert-butyldibenzylcarbazide, 4-tert-butyl-4'-decyloxy bis-indenyl, 2 , 4-dimercaptobenzylidene methane, 2,5-dimethylbenzyl decyl decane, 4,4,-diisopropylbenzylidenemethyl, 2-methyl-5-isopropyl- 4,-decyloxydi-denylmethane, 2_mercapto_5_t-butyl-4'-decyloxy Benzylmethane, 2,4-dimethyl-4, methoxydibenzylhydrazine, and 2,6-dimethyl-4-tert-butyl-4,-decyloxy In another embodiment, the first portion that absorbs ultraviolet light is a portion that absorbs 1; ¥_]8. "The portion that absorbs UV-B" means that the portion is in the ϋν_Β portion (29〇nm to 320nm) ) has a considerable appreciable absorbance in the ultraviolet spectrum. In a specific implementation, except for the wavelength range of 290 nm to 320 nm, as a part of the absorption of uv_b ^, it is appropriate to absorb the above part of the absorption. Examples of the UV-B moiety include 4-aminobutyric acid and its sputum, o-amine alum acid and its alkyl ester, salicylic acid and its alkyl ester, hydroxycinnamic acid and its alkane 201014610 vinegar 'di-based, two Carboxyl, hydroxycarboxydiphenyl ketone and its alkyl ester or acid halide derivative 'dihydroxy, dicarboxy, hydroxycarboxyl ketone and its alkyl ester or acid halide derivative 'dihydroxy, dicarboxy, hydroxycarboxy Bean and its alkyl ester or acid self-derivative derivative, benzalmalonate, benzimidazole derivative (such as phenyl benzimidazole sulfonic acid, PBSA) Benzooxazole derivatives, and other suitable functionalized species capable of copolymerizing in the polymer chain. Particularly suitable for UV-B absorption include UV-absorbing diphenylketone and UV-absorbing diphenylcyanoacrylate Derivatives. Examples of diphenyl ketone derivatives include those known in the art to provide skin protection from uv radiation, such as taught by usp ❹ 5,776, 439. Preferred compounds include 2 ___ methoxy diphenyl ketone ("hydroxyl Oxybenzone and 2,2'-dihydroxy-4-indolyl diphenyl ketone ("dioxybenzone") and diethylamine hydroxybenzyl benzyl benzyl vinegar ( Examples of the "hydroxybenzophenone" quinone diphenyl cyanoacrylate derivative include 2-ethylhexyl cyano-3,3-diphenyl acrylate ("Oclin" (〇 Ct〇crylene) Its derivatives. In a specific embodiment, the UV absorbing polymer comprises a sigma enthalpy of mono-absorption © u V . In this embodiment, the portion of the single absorption is preferably the portion that receives the UV-A, preferably the three saliva that absorbs uv. . In addition to the portion that absorbs UV, the first heavy unit (Α) of the polymer absorbing υν usually contains a functional group R' which may be, for example, a ruthenium atom, an alkyl group (= Ci-Cu) or the like. In a specific example, R has a molecular weight of less than about, such as less than about 50, such as less than about 3 Torr. In a preferred embodiment, Han, methyl. The R' group preferably has no UV moiety. Ma 12 201014610 The first repeating unit (A) may have a molecular weight of from about 150 to about 1 Torr, preferably from about 200 to about 7 Torr, more preferably from about 200 to about 500. The number (n) of first repeating units per molecule (e.g., average) may range from about 6,000 to about 6,000, preferably from about 2 to about 3,500, more preferably from about 5 to about 25, and even more preferably from about 10 to about 15 Torr. Hey. The polymer that absorbs ultraviolet radiation typically comprises a m mole second repeat unit (B). The second repeating unit (B) typically comprises a second pendant group r2 which is bonded to the C-C backbone by, for example, an ester linkage. The number of first repeating units (m) may be from about 2 to about 6,300, preferably from about 3 to about 4,000, more preferably from about 1 to about 30, and even more preferably from about 20 to about 3,000 per molecule (e.g., average). 2〇〇〇. In one embodiment, the second suspension base is a "pitch base" (which is a group) that is used to provide an appropriate amount of space between the absorbent portions (R) in which the uv polymer is absorbed. In this embodiment, the second suspension base has no UV absorbing portion. Thus, the second pendant group can also be used to promote intimate mixing with other components of the composition, such as hydrophobic components. Preferably, the spacer base sufficiently maintains the hydrophobic character of the polymer. However, the spacer group should not impart such an aberrant hydrophobicity that it is difficult to dissolve, disperse, emulsify, or otherwise stabilize the adsorbed polymer phase in a cosmetically acceptable carrier. Thus, the second suspension group (R2) of the second repeating unit (8) may comprise any one or both of the following: (1) at least one diarrhea do-) linkage 'for example, i to about 50 Weiyuan linkages, preferably about 1 to about 20 oxygen-fired linkages, more preferably from about i to about 2 石 石 oxy-oxygen linkages, even better from about 1 to about 16 oxime-oxygen linkages, even better 2 to 15 Shi Xi 13 201014610 It is best to have 2 to 5 oxyalkylene linkages, even better 2 to oxime oxygen linkages. Spontaneous Oxygen Burning Bonding In another preferred embodiment of the present invention, another specific shot, Wei burnt bond is a linear arrangement; in an organic functional group, such as a burnt group, a branch. The yoke oxygen linkage can terminate in the hydrocarbon portion of the intermediate number of carbon atoms. two. (11) A hydrocarbon moiety, for example, having a C7-C16 alkyl group. Preferably, the present invention comprises a c7-c16 hydrocarbon moiety, as exemplified; in another embodiment, the hydrocarbon moiety is linear. The second repeating unit B also comprises a second 771. And the same as the first repeating unit A -~: the group may be the same or may not be, for example, a hydrogen atom, an alkyl group (such as a group R, that is, a second functional group R' R, having a molecular weight of less than about 1 〇 〇, Example 1 such as 1) and so on. In a specific embodiment, in a preferred embodiment, R is a thiol group. For example less than about 30. The molecular weight of the second repeating unit (B) = there is: the portion to be collected. Ok, please go to about 50. , better about two = 10. To Yoru is more than %d : 2: 22 公 is suitable for blending into local defense _. Absorbing the body. h "Fengsheng" means that the percentage of moles of the first repeating unit (n) to the total enthalpy (n+m) may range from about 1 G% to about 8% (when the percentage is 100%, the pitch base is completely absent) - The polymer that absorbs _^ in this case may be a suspension of the homopolymer "c-c backbone and having - or a plurality of portions that absorb uv, but without the suspension base i of the portion without uv absorption. In some preferred embodiments, the molar percentage of the first repeating unit (η) to the ί repeating unit (n+m) ranges from about 5% to about or 201014610. In the specific example, for example, about 7.7%. The total repeating unit ― /0 芏 is about 40%, for example, 30% to 40%. The absorbing UV-absorbing polymer in the case of the heavy soul-term is not different from the above, and the polymer absorbing UV radiation is repeated early. In another embodiment, m2 includes - an additional repeating unit. The ❹rA repeating unit has an ultraviolet-absorbing group, an outer layer of oxalic acid or another organic moiety, or a combination of such groups. , to the extent that the base can be bonded to the C-C backbone. The second class that additionally absorbs ultraviolet: L, upper? and exists in the repeat The first ultraviolet absorbing susceptor of element a; ^ f 4 (four). Examples of the UV absorbing group include benzotrisyl and diphenyl bribe. In the other (d), the ultraviolet absorbing group is additionally absorbed. It can be used to collect and distinguish the spectral range different from the ultraviolet-absorbing group. The repeating unit A, the repeating unit B and the additional repeating unit can be arranged in various ways. For example, the repeating unit can be arranged in an alternating, various number of repeating units. Blocks, or in random arrangement. The molecular weight of the polymer that absorbs ultraviolet light is sufficiently high enough to reduce the possibility of absorption into the skin and thus the body. In one embodiment of the invention, the molecular weight of the polymer that absorbs ultraviolet radiation is greater than Approximately 2000<> In another embodiment, the molecular weight is sufficiently high to reduce the likelihood of absorption into the skin, but not so high that it is difficult to dissolve, disperse, emulsify, or otherwise stabilize the UV-absorbing polymer phase. In a cosmetically acceptable carrier, the UV absorbing polymer may have a molecular weight greater than about 2,000, but not so high that the polymer becomes crosslinked, and the polymer is uncrosslinked. The molecular weight of the UV polymer 15 201014610 may range from about 2,000 to about 10,000 Å, 〇〇〇, 较好, preferably from about 50,000 to about 750,000, more preferably from about 50,000 to about 500,000. In one embodiment, the polymerization The material is a linear polymer (ie, does not contain a considerable branch different from &, &, and R). In order to reduce the possibility of penetration of low molecular weight species into the skin, the polymer that absorbs ultraviolet radiation may have A large fraction of low molecular weight species, less than about 5%, such as less than about 1%, such as less than about 〇丨%. "Low molecular weight species" means species having a molecular weight of less than about 2,000. Cloth and water repellency, uv-absorbing polymers can have low water solubility in the specific examples. For example, in several embodiments, the ultraviolet radiation absorbing polymer can have a water solubility of less than about 3% by weight, preferably less than about 1% by weight. "Water-soluble" means that the polymer (proportional to the addition of water to the polymer) can be placed in 100 grams of deionized water and agitated to obtain a clear solution and remain visually homogeneous at room temperature and preferably transparent for up to 24 hours. Percentage by weight. Further, in several embodiments, the uv-absorbing polymer is desirably free of the free portion typically present in the so-called "polymer latex" composition to promote dispersion of the polymer in the aqueous system. Particular examples of the specific examples herein include anions such as sulfate, hybrid, nucleus, and phosphonate; and cations such as ammonium (including single...two and three species) "than bite" Scorpion rust, rust rust, poly (extension), bismuth ions, such as ammonium sulphate salt, recorded silk neonate salt, secret acetic acid. No swimming _ points of the absorption (four) compound can be used in waterproof coating Layers and improved spreadability. R vs. 16 201014610 Polymers that absorb UV radiation can have a sleek point or glass transition temperature, for example below about 37 ° C. Further want to absorb UV in polymers with absorbance in uv High enough to make it suitable for use as a sunscreen for humans. In a specific example, 'when the polymer is dissolved in a suitable solvent (such as DMSO, ethyl acetate, tetrahydrofuran, etc.) and spread or cast into a film, it has The molar extinction coefficient ❹ measured in the UV spectrum (and better in the UV-A spectrum) for at least one wavelength is at least about 1000 morknT1 'eg, at least about 2000 m 〇 1 - cm-i, such as at least about 4000 mol km 1, or Even 10,000 or 1 〇〇, 〇〇 Or 1,000,00 〇111 〇1-1 cm'1 ° The polymer of the present invention can be synthesized, for example, by methods known in the art. For example, a suitable polymer can be formed by addition polymerization, for example, via a suitable vinyl group. Free radical addition polymerization of unsaturated monomers. The resulting polymer may have repeating units in alternating, block, random, graft, star or other configurations. For example, the polymers of the present invention may be made to absorb The ultraviolet-based portion of the 10th ethylenically unsaturated compound (monomer) is prepared by reacting a second compound (monomer) comprising, for example, at least one azepine linkage in a specific example. In another embodiment, The second ethylenically unsaturated monomer comprises a hydrocarbon moiety, such as a hydrocarbon moiety having a median number of carbon atoms. This reaction can occur in the presence of an initiator, such as αιβν (azobisisobutyronitrile), or can be obtained as VAZ®® vA-40 is from Wilmingtcm, RI. DuP〇nt u, dioxin bis(cyanocyclohexane), or other suitable initiator. In one embodiment, the first genus Unsaturated compounds contain UV_ Part of a. The part which absorbs uv_A may be benzotriazole. Examples of suitable benzotriazole monomers include 2,_hydroxy_5,_ 17 201014610 methacryloxyethylphenyl-2H-benzotriazole And the methacrylated benzotriazole described in the following Examples 15 and 19. In another embodiment, the first ethylenically unsaturated compound comprises dibenzylhydrazine methane. The suitable monomer is the following invention The methacrylated dibenzyl fluorenyl oxime shown in Example 10. The first acetamino unsaturated compound may comprise a oxy-oxygen linkage, such as propyloxyalkyl polydimethyl oxime A suitable example of such a monomer is monomethacryloxypropyl polydimethyl decane (mpDMS), for example mPDMS having an average of about 1 decane linkage. Suitable other monomers comprising a decane include ^C^HwOsSi4~2-acrylic acid-2-methyl-3-[3,3,3-trimethyl-l,l-bis[(trimethyldecyl) Oxy]-1 -dioxaxyalkyl]propyl ester (also known as "TRIS" monomer). mPDMS and TRIS are commercially available from Morrisville, Pennsylvania's Gelest

Inc. In another embodiment, the second ethylenically unsaturated compound is an ethylenically unsaturated organodecane. "Ethylene-unsaturated organodecane" means any of a variety of compounds comprising at least one terminal Si-0-R linkage in other functional groups, wherein R is a functional group such as an alkyl group, an aryl group or an aromatic filament. Particularly suitable for B. sinensis. Unsaturated organic smoldering is methyl propyloxypropyltrimethoxy zebra (which has 3 oxime linkages from the common shixi atom), commercially available as Z-6030 from Midland 'd〇wc〇rning of Michigan. In another embodiment, the second ethylenically unsaturated compound comprises a hydrocarbon moiety, such as one having a median number of carbon atoms. Suitable examples include acrylate or mercapto acrylates having a C7-C16 conjugate* attached thereto. Examples include c8 acrylic acid vinery such as isooctyl acrylate h2c=chco2(ch2)5ch(ch3)2; 18 201014610

Ci2 mercapto acrylate, such as methyl propyl acid laurel vinegar η / - c (ch3) co2 (ch2) uch3; Isooctyl acrylate and lauryl methacrylate are commercially available from St. Louis, Sigma-Aldrich, Missouri. Alternatively, the UV absorbing polymer can be prepared by post-polymerization of the pendant to the polymer. For example, an acrylic acid polymer having maleic anhydride functionality can be synthesized, after which the polymer is reacted with a UV monomer such as benzophenone to chemically attach the UV-absorbing moiety via an ester linkage. Suitable maleic acid needle copolymers include, for example, PA-18 (octadecene/maleic anhydride copolymer) commercially available from Chevron Phillips, or Gantrez AN copolymer commercially available from ISP (PVM/MA). Copolymer). Alternatively, N-hydroxysuccinic acid diamine of (meth)acrylic acid can be used as a starting monomer. The polymers of the present invention can be used, for example, by combining a polymer with a cosmetically acceptable carrier as described below. Incorporation of the polymer of the present invention into the composition provides for enhanced SPF (primary UV-B absorbance), enhanced PFA (primary UV-A absorbance), or both. Topical Composition In one embodiment, a composition is provided, such as a composition suitable for topical/cosmetic use applied to a human body, such as a keratinaceous surface, such as the skin or hair, particularly the skin. The composition comprises the UV-absorbing polymer of the invention described herein. The concentration of the UV-absorbing polymer of the invention may vary from 0.001% by weight to about 1% by weight, preferably from about 1% to about 50% by weight, more preferably from about 0.5% to about 40%. The compositions useful in the present invention are useful in a variety of cosmetic applications, including the special 201014610::5 vine skin free of UV radiation. The composition can therefore be made into a wide variety of transmissions. The form includes, but is not limited to, an emulsion (W/O, 〇/W or a mixture of liquids, dispersions, solutions, or coatings on water or water-insoluble substrates (eg, organic or inorganic powders, fibers, Or the base of the film. Suitable for lotion, cream, gel, stick, spray, ointment, mousse, daily etched composition can be used for various end uses, such as leisure or sputum = sunscreen, moisturizer, Cosmetics, detergents/toners, anti-aging products σσ, or combinations thereof. The compositions of the present invention can be prepared using a teaching method well known to artisans, such as those skilled in the art of cosmetic formulation. The composition of the invention comprises water and is therefore a seven-sex composition. In several preferred embodiments, the composition is an emulsion comprising an aqueous phase and an oil phase. Particularly preferred is that the composition comprises a stable (preferably chyle) a continuous aqueous phase of a UV absorbing polymer. The oil phase may be present in the emulsion as a non-attached droplet or unit having an average diameter of from about 1 micron to about 1 micron, preferably from about 1 micron to about 100. Micron. The composition comprises a continuous (preferably emulsified) continuous oil phase of water. The percentage of water contained in the beta composition may range from 1% to about 99%, preferably from about 20% to about 80%, more preferably. From about 30% to about 70%. The second UV absorbing polymer is in a particularly preferred embodiment 'the composition comprises a second UV absorbing polymer. The second UV absorbing polymer means to absorb UV with the above. a compound that chemically distinguishes (on a chemical formula, such as a chemical formula or a repeat unit content). Broadly speaking, a second UV-absorbing polymer can have a variety of chemical backbones (such as a naphthenic or c-c) and One or more UV-absorbing portions (UV-A and/or UV_B) are suspended at one or more molecular ends or from the backbone. The second UV-absorbing polymer may have at least 2, more preferably at least about 10 Repeating unit. In a specific example, in order to enhance the synergistic effect between the uv-absorbing polymer of the present invention and the second absorbing polymer, the molecular weight of the second UV-absorbing polymer is similar to that of the present invention. Polymer. Thus, the second 吸收 absorbs UV The polymer may have a molecular weight of at least 2000, such as at least about 5,000, such as at least about 10,000. In one embodiment, the second UV absorbing polymer has a molecular weight of from about 5,000 to about 2 Torr. The second uv-absorbing polymer may have a solubility characteristic as described above for a polymer similar to the absorption υν of the present invention (e.g., less than about 3% by weight water soluble, preferably less than about 1% by weight.) Apparel has found that first The UV absorbing polymer is combined with the second XJV absorbing polymer, wherein the first absorbing νν polymer and the second absorbing υν ❹ polymer have particular characteristics that surprisingly enhance UV absorbance. For example, in the present invention In one aspect, the composition of the present invention comprises a polymer comprising a first absorption υν that absorbs a portion of UV-A and a polymer comprising a second absorption uv that absorbs UV_B. The portion that absorbs UV_B is different from the portion that absorbs UV-A. The first UV absorbing polymer and the second UV absorbing polymer are characterized by being capable of providing both a synergistic SPF and a synergistic PFA, the first and second UV absorbing polymers having a mass percentage ranging from at least about 40/6 ( , 羲 as follows). In a preferred embodiment, the first uv-absorbing poly-sigma and the first-absorbing uv polymer are characterized by being capable of providing synergistic spF and 21 201014610 synergistic PFAs having a protection ranging from at least about 6% by weight throughout the mass percentage range. To evaluate whether a particular combination of two UV-absorbing polymers provides synergistic SPF protection, the following logarithmic SPF procedure can be used. The SPF is determined for a particular blend of (a) the first UV absorbing polymer, (b) the second UV absorbing polymer, and (c) the first UV absorbing polymer and the second UV absorbing polymer. It was decided that the SPF was evaluated by forming a film with the polymer or composition to be tested' and using the following IN-VITRO SUN PROTECTION TEST METHOD. In particular, 'if the SPF of each UV-absorbing polymer (Polymer A and Polymer® B) is a blend of SPF pairs higher than the sum of the logarithm of the unblended polymer components, the weights are multiplied by A specific blend of UV-absorbing polymers provides synergistic SPF protection for the respective mass fractions of the total mass of the two UV-absorbing polymers. The efficiency conditions are therefore stated as follows:

Log SPF 推物>XA Log SPFa+Xb Log SPFb For example, if the polymer SP has a Log SPF of 1 and the polymer b has a Log SPF of 1.2 'two polymers (40% polymer A, 60% polymer) The blend of B) has a Log SPF greater than: ❹ [(0.4) X (1)] + [(0.6) X (1.2)] = 1.12 The special blend provides a synergistic SPF. Similarly, synergistic PFA is determined in the same manner. If the Log PFA conjugate >Xa Log PFAa+Xb Log PFAb special blend provides a synergistic PFA. Like SPF, PFA is determined according to the following in vitro sun protection test method. 22 201014610 If two uv-absorbing polymers can be blended into a single phase (with solvent systems or with no different components) and the blends are both for synergistic SPF and synergistic PFA protection, then The special blend of polymer human and polymer b "can provide both synergistic SPF and synergistic PFA protection. "Solvent system" means a solvent or a solvent capable of simultaneously dissolving two uv-absorbing polymers throughout a concentration range, A blend of oil, plasticizer, and the like. Furthermore, if polymer A and polymer B are capable of targeting two polymers to three different mass ratios (preferably at least four different mass ratios, more preferably at least about five different mass ratios, and the measured mass ratios) Preferably, the synergistic SPF and the synergistic protection are provided by at least 10% separation, such as 80%/20 and 70%/30), wherein the lowest concentration of the polymer A and the southernmost value of the polymer A are With about 40% separation, the two polymers are capable of providing synergistic π? and synergistic PFA assurance, both of which have a mass percentage range of at least about 40% throughout the two polymers. Likewise, if at least three different mass ratios are separated by at least about %, the UV absorbing polymer can provide both a synergistic SPF and a synergistic PFA 〇 protection of at least about 60% over the mass percentage of both polymers. For the purpose of efficiency assessment, 'about X%' means within. In several preferred embodiments, (a) the first UV absorbing polymer is a UV absorbing polymer according to the present invention, that is, the first UV absorbing polymer comprises a C-C backbone, and includes an absorption UV-A. a portion of the first pendant base' and further comprising a second suspension "pitch" group comprising a siloxane coupling and/or a medium number of carbon atoms; and further (b) the second UV absorbing polymer comprises a different absorption Part of UV-A that absorbs UV-B. In a preferred embodiment, the second UV absorbing polymer also comprises at least 23 201014610 - a Si-O- linkage, which is preferably a degree of partial Wei Shao shaft. In a specific embodiment, the oxoxane backbone has at least about 1 fluorene linkage, e.g., at least about 50 oxane linkages. In a preferred embodiment, the second UV absorbing polymer is dimethicodiethyl benzal malonate 'also known as bismuth adipic acid a ruthenium, for example Known as the sputum of Ju Shi Xi Oxygen-15. Examples of suitable benzalmalonates are described in USP 6,193,959 to Bernasconi et al. Particularly suitable for benzalmalonates comprises PARS® L SLX, commercially available from Heerlen's Netherlands DSM (Royal DSM N.V.).申请人 Applicants have discovered that by utilizing a blend that exhibits synergy across a wide range of mass ratios, it is possible to provide advantages in enhancing protection with both non-penetrating sunscreens and across UV-A and UV-B protection. Composition. In another embodiment, the composition comprises a first UV absorbing polymer and a second UV absorbing polymer capable of providing both synergistic spf and synergistic PFA protection over a range of mass percentages of the two polymers. 4 〇%; the composition further contains a solvent system that promotes synergy. "Promoting solvent system" means the following: solvent system When used to dissolve UV absorbing polymers, ❹ UV absorbing polymers provide synergistic blends. In addition to promoting a synergistic solvent system, the composition may have one or more other types of ingredients suitable for the personal care composition. A solvent system that promotes synergy can be selected to dissolve both UV absorbing polymers. Thus, the components of the solvent system may have dissolution parameters similar to those of the uv-absorbing polymer. In one embodiment, the solvent system that promotes synergy comprises, consists essentially of, or consists of: non-absorbing violet 24 201014610 A solvent or plasticizer that is externally radiated and has a dielectric constant (i.e., a static dielectric constant measured at 20 ° C) of from about 3 to about 8 (more preferably from about 3 to about 6, or even more preferably from 4 to 6). Examples of suitable solvents are described in the U.S. Patent Application Serial No. 20090098367, entitled "Composition of Elongated Particles with Diversified Charges and Aspect Ratios" [0060], which is incorporated herein by reference. In several embodiments, the solvent is selected from the group consisting of benzyl esters, such as alkyl benzyl esters, particularly C12-C24 alkyl esters of benzylic acid, such as Cu-Cb esters, which have a dielectric constant. 3.8 of FINSOLVTN, commercially available from Elmwood Park, Finex Inc. of New Jersey; dibutyl adipate (such as CETIOL B having a dielectric constant of about 5.1, commercially available from Ambler, Cognis Corporation of Pennsylvania) ; octanoic acid/capric triglyceride (having a dielectric constant of about 3.8); and combinations thereof. In another aspect, the composition of the present invention comprises a first UV-absorbing polymer comprising a UV-A absorbing portion and a second UV absorbing polymer comprising a UV-B absorbing moiety, wherein the first UV absorbing polymer The polymer having a PFA/SPF ratio greater than 0.3 and the second UV absorbing has a PFA/SPF ratio of less than 0.3. By selecting the first UV absorbing polymer and the second UV absorbing polymer to meet these requirements, it is possible to complete a composition having a PFA/SPF approximation or equal to 0.3, thus providing broad spectrum protection. The first UV absorbing polymer can be a UV absorbing polymer of the present invention. However, the first UV absorbing polymer may have a decane backbone and/or have a spacing base between the polymers that absorb UV in the present invention and/or have no spacer groups. Furthermore, in order to increase the size of both SPF and PFA and further provide a composition with broad spectral protection, the applicant has found that the desired composition not only contains 25 201014610, but also has a PFA/SPF ratio of greater than 0.3 with UV-A absorbent. a UV absorbing polymer and a UV absorbing polymer having a UV-B absorbing agent having a PFA/SPF ratio of less than 〇3, and a special mass ratio of the two UV absorbing polymers in their presence. Both synergistic SPF and pFA protection are available. In this way, the SPF and PFA sizes are increased, but the ratio of removal from 0.3 is not relied upon. In a related embodiment, the composition further comprises a solvent system that promotes synergism. In another aspect, the composition comprises a first UV absorbing polymer having a C-C backbone and comprising a UV-A absorbing moiety, and a second having a decane backbone and comprising a UV-B absorbing moiety. UV absorbing polymer. The first UV absorbing polymer can be formed by reacting two or more ethylenically unsaturated monomers. Thus, it may have a first suspension base comprising a portion of absorption 1; It may further comprise a second suspension base, such as a pitch base. In a specific example, the first uv-absorbing polymer is the uv-absorbing polymer of the present invention. The second UV absorbing polymer can have a variety of configurations. In a specific example, the portion that absorbs UV is present at the end of the polymer. In a particular embodiment that is particularly desirable, the second UV absorbing polymer comprises a pendant comprising a portion that absorbs. Applicants have surprisingly discovered that a first UV absorbing polymer having a c-c backbone and a UV-A absorber is combined with a second UV absorbing polymer having a oxoxane backbone and a UV_B absorber for SPF and PFA provides a broad-based synergistic effect' and various other combinations of backbone types and UV absorber types (eg, polymerization with C-C backbone and UV-A absorbers) 26 201014610 with C-C backbone and UV absorption -Part of the UV-absorbing polymer combination) does not provide this desired feature. ❹

In another aspect, the composition comprises a first absorbent 1; a polymer having a backbone, a first base comprising a first uv absorber, and a second comprising a ruthenium to ί-Wei Weiji a suspension base, wherein the second suspension base has no chromophore; and a second absorption υν polymer comprising at least one diarrhea (as in its backbone, but this is not necessarily required) and different from the first absorption UV The second part of the part absorbs the part of υν. Under the circumstance of being bound by theory, the applicant believes that the presence of the first suspension group of the first absorption υ ν 之 氧 氧 增进 增进 增进 增进 增进 增进 增进 增进 增进 增进 增进 增进 增进Insula absorbs UV radiation to provide enhanced energy. In a preferred embodiment, the second υν absorbing polymer comprises at least one of the oxy-sinter (Si-0-Si) linkages to the extent that it can be partially oxidized. In the specific item, Wei (4) dry has at least about 1G of oxygen-burning bonds, for example, at least about 5G of oxygen-burning bonds. In a preferred embodiment, the UV-absorbing polymer comprises a sub-base malonate as the group of the absorption group. + Particularly suitable for the case of the phyto-diethyl propyl malonate, also known as sub-densylmalonic acid (tetra) oxo, such as the filter known as "Juqian·15". Examples of oxygen suitable for smalonate include the usp (10) narrator of BemaseQni et al. It is especially suitable for the sub-section of the second (four) including WLSLX", discussed from the face of the Netherlands DSMN.V.). In another embodiment, the second uv-absorbing polymer comprises a 2-nitro group 27 201014610 -3,3-diphenyl acrylate functional group, as present in usp 6,962,692, IJSP 6,899,866, and/or 1^? 6,800,274 The polymeric sunscreens disclosed therein, comprising adenic acid, 3·[(2-nitro-1-oxide-3,3) polymerized with 2,2-mercapto-1,3-propanediol -Diphenyl-2-propenyloxy]_2,2-dimercaptopropyl-2-octyldodecyl ester. This polymer has a low molecular weight (less than 2 Å) and is sold under the trade name "POLYCRYLENE", commercially available from the HallStar Company of Chicago, Illinois. In another embodiment, the composition further comprises a Or a plurality of inorganic ultraviolet shielding compounds', for example, inorganic oxides comprising titanium dioxide, oxidized iron, iron oxide. In one embodiment, the composition has no monomeric sunscreen. In another embodiment, the composition may further comprise one or more additional UV-A and/or UV-B absorbers. Examples of such absorption/reflecting agents include, but are not limited to, "monomers". Organic UV filters: decyloxycinnamate derivatives such as methoxycinnamic acid octyl vinegar and methoxycinnamic acid isovalerate; camphor derivatives For example, 4-methyl subunit-based rod brain, camphor benzalkonium 0 methosulfate, and bismuth diterpene sulfonic acid; salicylate derivatives such as octyl citrate, triethanolamine (trolamine), salicylate, and homosalate; sulfonic acid derivatives, such as phenylbenzimidazole; benzophenone derivatives, such as benzophenone, diphenyl ketone 4 (sulisobenzone), and oxybenzone; benzylic acid derivatives, such as amino-based acid and octyldimercapto-aminobenzyl acid; octocrylene and other β,β-diphenyl acrylate; Octylbutyric acid tricoterone; octyl triterpene ketone; butyl methoxy dibenzyl decyl decane; decyltrizole trioxane; and o-amine benzene 28 201014610 capric acid caprate. Other suitable uv absorbers/reflectors useful herein can be found in Sagarin, Cosmetics Science and Technology, Chapter VIII, Dreading and the following and the/C/ from m must be, page 1672. A list of such compounds is also disclosed in U.S. Patent 4,919,934. In a number of specific examples, the composition may comprise one or more compounds suitable for enhancing photostability. The light stabilizer comprises, for example, a diester or a polydecyl ester of naphthalenedicarboxylic acid. An example of a diester or polyester of naphthalenedicarboxylic acid is a compound of formula (X) or (XI): (X)

Wherein R10 and R23 are independently selected from the group consisting of LG County, a diol having a structure of HO-Ru-OH, and a polyethylene glycol having a structure H〇Ri7_(_〇_Ri8_)m5 〇H; Rl7 and ' Independently c "C6 alkenyl; m5 and m6 are each independently in the range of about 4 _. Examples of the naphthalene bismuth vinegar or polyfluorene (including synthesis) are described & usp 5,993,789, which is included (but (HALLBRITE TQ » CP Hall Company j Bedford Park >>#». -r, , Λ Illinois, USA). See Bonda 29 201014610 et al 'Allured's Cosmetic & Toiletries Magazine,] Λ5{6) ·· 37 to 45 (2000) discloses the use of such compounds in an anti-caries agent. In one embodiment, the diester or polyester of naphthalene dicarboxylic acid may range from about 0.1% by weight to about 3% by weight of the total composition (eg, about 1% by weight to about 10% by weight. Other light stabilizers suitable for other light stabilizers include butyl octyl sulphate, bemotrizanol, hexyl syringyl malonate, hydrazine (tetramethyl) Hydroxycitidin) citrate, polyester-8, octocrylene, ethylbenzylidene camphor, oxybenzone, guanamine oil, Alkyl benzyl esters "In one embodiment, the composition further comprises a benzyl alkyl ester acid derivatives thereof Examples of the benzyl ⑩ acid alkyl ester derivative is a compound of formula (XII) or (ΧΠΙ):. (XII)

OH

C Ο 〇—CH2—CH—(CH2)m7—ch3 ^η^2η+1

Where m7 is 5, 7, or 9, and η is 4, 6, or 8; (XIII)

〇一CH2—CH—(CH2)m8—CH,

CpH2p+i wherein m8 is 5 or 7, and p is 4 or 6. The compound formulas (乂11) and (乂111) can be formed by typical esterification and transesterification reactions as described in 1;8-5,783,173. An example of this long branched chain of sulphuric acid vinegar is disclosed in USP 5,783,173 and includes, but is not limited to, butyl octanoic acid 30 201014610 ester (HALLBRITE BHB, C.P. Hall Company, Bedford Park, Ill.). In one embodiment, the alkyl benzoate derivative can range from about 0.1% to about 30% by weight total composition (e.g., from about 1% to about 10% by weight).

The composition of the present invention may further comprise one or more cosmetic preparations (two doses of "cosmetic active agent") which are compounds which have a cosmetic or therapeutic effect on the skin, such as a medicament for treating wrinkles, acne or lightening the skin. The agent is selected from, but not limited to, a group consisting of: hydroxy acid; benzamidine peroxide; resorcinol sulfur; D-panthenol; hydroquinone; anti-inflammatory agent; skin lightening agent; And antifungal agents, such as miconazole, clonazole, and dubial; vitamins such as ascorbic acid; tocopherols and bismuth-reactive phenols, such as retinoic acid acetate, retinol-like Alcohol, retinal aldehyde, palmitic acid rectification ester, acetic acid reticulum S, and reticulum acid; hormones, such as eosin and dimension, diketone ' 2 -methylaminoethanol; lipoic acid; amino acid For example, valine and amide 酉夂 'lactose acid' self-tanning agents, such as diacetone; dimethylaminoethanol, vinyl lion A; secret acid; riboflavin; side; ribose; .NADH and FADffi; herbal extracts such as ginkgo, ,, stomach And derivatives thereof. The cosmetic active agent will typically be present in the compositions of the present invention in an amount of from about 2% by weight to about 1% by weight, such as from about 5% by weight to about 5% by weight of the composition. 2 includes; 1 but not limited to) (1) alpha by acid, such as indole acetic acid, and / or (.. 夂 豕 豕 豕 、, and tartaric acid, (ii) puic acid, such as 夂 夂 $ m tannic acid. See, for example, European patents Application No. 2, Moving. 31 201014610 Examples of ascorbic acid derivatives include, but are not limited to, ascorbyl palmitate, magnesium ascorbyl phosphate, sodium ascorbate, zinc ascorbate, ascorbyl ascorbate, sodium ascorbate, and ascorbic acid Peptides. Examples of hydroquinone derivatives (but not limited to) arbutin ^ The compositions of the present invention may also include one or more of the following: antioxidants (such as ascorbic acid, tocopherol, polyphenols, double bond retino, BHA, and BHT) ), chelating agents (eg EDTA), and preservatives (eg, benzylic acid esters). Examples of suitable antioxidants, preservatives, and chelating agents in the, c/, 1612-13, 1626, and 1654-55 Page. In addition, this Useful ❹ The topical composition may contain conventional cosmetic adjuvants such as dyes, opacifiers (such as titanium dioxide), pigments, and aromas. One or more UV-absorbing compounds in the composition may be combined with a "cosmetic acceptable topical carrier". That is, a carrier for topical use, which is capable of having other components dispersed or resolved therein, and possessing the properties that make it safe for topical use. Thus, the composition may further comprise any of the various functionalities known in the art of cosmetic chemistry. Ingredients, for example, emulsifiers, lubricants/oils/蠛, humectants, thickeners, opacifiers, aromas, dyes, co-solvents in other functional ingredients. • The composition may not substantially render the composition unsuitable for localization. The ingredients used. Thus, the composition may be substantially free of solvents, such as volatile solvents, and other volatile organic solvents such as, for example, propylene, xylene, hydrazine, and the like. "Substantially absent" means that the ingredients are present individually or in combination at a concentration of less than about 2%', preferably less than about 1%, more preferably less than about 5%, preferably no such compound. In several embodiments, the composition has a pH of from about 4 Torr to about 8 Torr, preferably from about 5.5 to about 7.0. 32 201014610 In a particularly noteworthy specific example, the composition comprises an emulsifier suitable for stabilizing the uv-absorbing polymer, such as an oil emulsion in water. Suitable emulsifiers (e.g., nonionic emulsifiers) include those typically used in personal care products, such as alkyl/fatty alcohols, alkyl/fatty esters, alkyl/fatty glucosides, alkoxylated ester fatty acids, and the like. In another embodiment, the composition comprises one or more oils or other hydrophobic compounds to assist in spreading and or dissolving the polymer that absorbs uv. Suitable hydrophobic compounds include oils, including mineral oils, paraffin fats, oils derived from plants or animals (triglycerides, etc.); non-hydrocarbon based oils such as dimethicone, and other oxygenated oils. And aerobic glue; aroma oil; wax, including polyethylene wax, and other mixtures of fatty esters, non-essential glycerin 酉I. The compositions of the present invention can be used by topical administration to a mammal, such as by laying or spreading the composition directly onto human skin or hair. The composition of the present invention can be prepared by a teaching method well known to those skilled in the art. Specific examples of the inventive polymers, methods, and compositions are described below. The composition according to various embodiments of the present invention confers one or more important advantages when compared to prior art compositions. According to several specific examples, the composition comprises a UV-absorbing polymer having a C-C backbone and such a more flammable backbone typically confers various advantages. Such advantages include, but are not limited to, greater flexibility in formulation (emulsion, solution, bulk solution), and/or ability to initiate and/or manufacture higher molecular weights and modify molecular weight and distribution thereof, and/or reduce It is contaminated by unreacted monomers. Other potential advantages include the ability to modify the UV-absorbing chromophores and the ability to suspend the configuration and sequence of the 2010 矽 烷基 alkyl group to enhance the likelihood of achieving a high enough uv chromophore level to the desired combination of polymers, thereby reducing The concentration of polymer required in the final topical sunscreen composition' thus creates a variety of sunscreen formulations. Applicants have also surprisingly found that UV absorbing polymers in accordance with several embodiments of the present invention can be made with the appropriate molecular weight necessary to reduce skin penetration. They can also be made sufficiently hydrophobic to avoid insufficient water repellency (which can be common in polymer lattices or polymers with excessive hydrophilic properties), yet still be easily formulated and have sufficient spreadability on the skin. , but still can be economically manufactured.

Furthermore, according to several specific examples of the present invention, the C-C backbone, absorbs UV

The polymer has the ability to blend with other UV-absorbing materials to create the desired balance of UVA/UVB protection. The blend can also be more aesthetically pleasing when it is not necessary to formulate additional helium oxygen in the form of a helium oxide oil. The formulation achieves a high spread level and water resistance due to the low water solubility of UV absorbing polymers. The following examples further illustrate the invention. [Embodiment] Examples 1 to 3: Preparation of uv-absorbing polymer The following UV-absorbing polymer according to the present invention was synthesized according to the following method: an ethylenically unsaturated monomer (herein referred to as "NORBLOC") was dissolved in acetic acid B. The ester solvent was added to a three-necked l〇〇ml round bottom flask containing a UV-absorbing base having a molecular weight of 292 g/mol. (2,_hydroxy-5'-mercaptopropenyloxy group) Ethylphenyl)-2Η-benzotriazole. Then add 25g of the 34th 201014610 diethylenically unsaturated monomer-monomethacryloxypropyl polydimethyloxane (mJPDMS - containing 1 oxime repeating unit per molecule; molecular weight of about 900g / mol) . The reaction mixture was stirred at 65 ° C (± 15 ° C) under reflux until completely dissolved and flushed with nitrogen for 30 minutes. Then, azobisisobutyronitrile (AIBN; molecular weight 14.6 g/m〇l) was added using a syringe. The reaction was stirred for 16 to 18 hours and the loss of NORBLOC was monitored by TLC. Once the reaction was complete, 1 Torr to 200 ml of toluene was added to the mixture while stirring and heating to 8 Torr. The crucible was cooled to ambient temperature, and 5 ml of ice-cold methanol was added to precipitate the polymer. Two additional wash precipitates were performed with 500 ml of ice-cold methanol to remove any unreacted monomer. The precipitate was dissolved in ethyl acetate, concentrated by rotary evaporation and placed in vacuo for 24h. The amounts of the solvents used to prepare the three polymers (Examples 1 to 3) were changed by changing the amounts of NORBLOC and AIBN to 4, 7, and 1 respectively. The weight of the reactant (i.e., NORBL0CAmPDMS) is shown in Table 1 below: _______ Table 1 Example Example 1 was implemented to % 3 hiPDmT 95^15% - 9135% ~

Norbloc 4.17% 8.00% 12 66% ΑΙΒΝ 68 68% 〇·65% The molar ratio calculated for the reactants of the same example. _______ Table 2 _, Far Example 3 35 201014610 mPDMS 83.33% 74.08% 64.56%

Norbloc 12.50% 22.22% 32.28% AIBN 4.17% 3.70% 3.16% The polymer was analyzed by gel permeation chromatography for various molecular weights and polydispersity. The results are shown in Table 3 below: Table 3 Examples Example 1 Example 2 Example 3 Mw 684,057 166,459 162,957 Μη 88,194 51,173 59,505 Μζ 3,480,297 478,776 425,511 Mw/Mn 7.76 3.26 2.74 MP 166,723 99,588 98,728 Mz+1 7,009,308 1,059,361 856,469 Dispersibility 7.68 3.28 2.65 θ Examples 4 to 8: Preparation of uv-absorbing polymer and NORBLOC homopolymers The UV-absorbing polymerizations according to the invention are similar to those of Examples 1 to 3 but the solvent quality is changed ( The amount of AIBN and NORBLOC was also changed in Example 4 as 5 g and Examples 5 to 8 in m. The preparation example 8 was used as J2SL-v bis-poly polymer (without mPMDS). The molar percentage of the reactants was given in the following table. 5: Table 5 Example Embodiment 4 Example 5 Example 6 Example 7 Example 8 __-___^Comparative) 36 201014610 mPDMS 80.0% 48.9% 29.8% 6.7% 0.00% Norbloc 16.0% 48.4% 68.1% 91.9% 96.4% AIBN 4.0% 2.1% 2.1% 1.4% 3.6% Example 9: UV absorbance at 5 weight percent chromophores - Comparison of UV absorbing polymers with NORBLOC conjugates. Example 6, Example 5 UV-absorbing polymer and real The homopolymers of Example 8 were each dissolved in TLF separately. The polymer concentration was chosen so that the color development in each case was 5% based on the total concentration of the solution. Each solution was tested according to the "External Sun Protection Test Method" described below. In vitro Sun Protection Test Method The baseline transmission of the PMMA plate (base) under the test material applied without any application was measured. Test samples were prepared by providing a polymer sample. (The blend can also be tested by this method. The polymer can be tested without any additional additives, in a solvent system, or as part of a personal care composition that can contain solvents and/or additional ingredients.) Use each sample. The square centimeter base was applied to a 2 μΕ solution and applied separately to a seesaw (available from Helioscience 'Marseille, France), and the operator's fingers were wiped into thin layers and allowed to dry. Three samples of this were completed for each test material. The samples were then allowed to dry for 15 minutes before measuring absorbance using a calibrated [讣邛"8 UV-1000S UV transmission analyzer (Labsphere, North Sutton, New Hampshire, USA). Absorbance measurements were used to calculate SPF and PFA index (UVA-based bioprotective factor ^ Calculate SPF and PFA using methods known in the art - see the following equation for SPF (丨): ° 37 201014610 \Ε{λ)*Ι{λ)^άλ ^ Nr- — A=290nm SPF^ - ΊΞ4ω^--(1) lE{X)*i{X)*m~^xUdx X—29Qnm where: Ε(λ)=red spot action spectrumΙ(λ)=from UV Source Received Spectral Irradiance λ(λ)==Test the average monochromatic absorbance of the product layer before UV exposure (1λ=wavelength step (lnm) © Calculate PFA (ie UVAPF) in a similar manner, but with a wavelength range of 320 nm to 400 nm. Figure 1 shows the absorbance spectra of the UV-absorbing polymers of Examples 5 and 6 and the homopolymer of Example 8. The PFA and SPF were calculated and shown in Table 6 below: Table 6 In the polymer solution Chromophore % SPF PFA in polymer % solution Example 8 5 5 7.2 5.9 Example 6 12.5 5 15.3 9 Example 5 20 5 15 7.6 The result indicates Each sample contained the same amount of total chromophores, and the copolymers of Examples 5 and 6 each containing "pitch" repeating units (mPDMS) were quite surprisingly higher than the homopolymers of Example 8 with higher SPF. And PFA. Thus, it was revealed that by using mPDMS as a comonomer, surprisingly advantageous improvements in UV absorption 38 201014610 were achieved compared to polymers lacking this spacing. Example ίο The following illustrative examples are provided for use. For synthesizing the UV-absorbing polymer of the present invention, the polymer is similar to the polymers of Examples 4 to 7, but the UV-absorbing group is dibenzylidene methane. Step 1 Protection of a phenol: In this step, arbutin The ketone is reacted with dihydropyran to protect the phenolic hydroxyl group.

Step 2 - Coupling reaction to prepare ?-diketone (condensation): In this step, a ?-diketone is prepared by preparing an enolate solution and adding an acid vapor dropwise. An excess enolate is used in proportion to the beta-diketone.

Step 3 - Deprotection of oxime ether

Step 4 - Methacrylate phenolation: In this step, mercapto acrylated dibenzyl decyl decane (ethylene unsaturated monomer) is prepared by esterification with mercapto acrylic anhydride. 39 201014610

Step 5 - Polymerization: Preparation of dibenzyl decyl decane and mPDMS acrylic acid in a similar manner to the synthesis of the above polymers (Reference Examples 1 to 4) (AIBN initiated polymerization 'addition via cold methanol precipitation) Copolymer. Example 11 The UV absorbing polymer of Example 3 was blended with a second UV absorbing polymer (PARSOL SLX). The polymer of Example 3, PARSOL SLX, and various blends of the two were tested for SPF and PFA. No additional components (such as solvents, oils, etc.) were added to the test sample. Table 7 below shows the results. Table 7 Polymer Blend SPF PFA PFA/SPF Example 3, pure 14.8 6.5 0.44 Parsol SLX 'Pure 16.7 1.1 0.07 50% Example 3 '50% SLX 64.7 6.4 0.10 60% Example 3 '40% SLX 34.5 4.8 0.14 80% Example 3, 20% SLX 47.0 7.8 0.17 95% Example 3, 5% SLX 27.8 7.5 0.27 96% Example 3, 4% SLX 23.9 7.0 0.29 98% Example 3 ' 2% SLX 28.4 8.4 0.30 Results It was pointed out that the blend of Example 3 and PARSOL SLX showed significantly better performance than either of the individual polymers when the total amount of sunscreen was controlled. This surprisingly points out that by UV-free polymer (having a C-c backbone, a suspended TJV-A group, and a spacer base) and a Wei-burn backbone polymer (with a free portion of the absorption) according to the present invention ( The blends with UV-B absorption of yttrium 2 provide synergistic UV absorbance. The results show that there is a further desirable (but typically difficult to achieve) high value SPF (eg greater than 2 〇), two A combination of PFA (eg greater than 5) and PFA/SPF high ratio (eg greater than 〇.2).

下列 The following personal care compositions shown below are prepared using emulsification techniques known in the art of cosmetic chemistry. The composition is an aqueous emulsion in oil (water as the outer j phase) and comprises two uv-absorbing polymers, an emulsifier for emulsification of UV-absorbing polymers (SIMUSOL, MNTANOV), a humectant (glycerin), and a preservative. , thickener (SIMULGEL polymer), and, adjuster. A main vessel is filled with water to which is added glycerin, p-hydroxybenzylate, and phenoxyethanol. Then gradually add the # vessel to 75t. An oil phase premix was prepared by mixing the polymer of Example 6 with PARS0L SLX and DC 246, SIMUS® L, jONTANOV, and cocoate BG. The oil phase premix was then slowly warmed to 75 ° C. Once the two vessels were reached, the oil phase premix was added to the main vessel. They were mixed for 15 minutes and kept in place. After Μ minutes, add SIMULGEL and mix for 5 minutes while keeping the instrument alone at 75 C. Then slowly cool the vessel to 3 (TC ' with citric acid or sodium hydroxide to adjust the pH between 5 and 6. Table 8 Trade name INCI or CTFA name to 曰n / repeat % 41 201014610 Water (water) Water (aqua 68 glycerol glycerol 3 p-hydroxybenzyl acid methyl p-hydroxybenzyl octoate 0.2 p-hydroxybenzyl propyl p-hydroxybenzyl acrylate 0.1 phenoxyethanol phenoxyethanol 0.7 inventive example (example polymer 10 6) Polymer PARSOL SLX Polyoxane-15 1 DC246 Cyclohexaoxane and Cyclosporine 3 SIMUSOL 165 PEG-100 stearate and glyceryl stearate 1 MONTANOV 68 Green stearyl alcohol and recorded Soil stearin glucoside 3 cocoate BG butane diol cocoate 10 SIMULGEL EG sodium acrylate/acryloyl dimethyl methic acid sodium 0.5 citric acid copolymer and isohexadecene and polysorbate vinegar 0.1 hydroxide Nano sodium hydroxide 0.1

The composition has good spreadability and leaves no fragile flaky residue on the skin.

Example 13A: Preparation of UV-absorbing polymer The following UV-absorbing polymer of the present invention was synthesized according to the following method. 4.6 g of the first ethylenically unsaturated monomer, isooctyl acrylate (h2C == chco2(ch2)5ch(ch3)2) (molecular weight 184 3g/mol) and 8g of NORBLOC were added to the three necks equipped with the addition funnel 5 〇〇ml round bottom flask. Then 50 ml of ethyl acetate was added. 74 g of isooctyl acrylate and 1 ml of ethyl ethane 42 201014610 acid vinegar were added to the addition funnel attached to the flask. The reaction mixture was at 65 under reflux. (: (±15. 〇 stirring until completely dissolved and flushed with nitrogen for 30 minutes. 2 〇〇 mg azobisisobutyronitrile (A] [bn; molecular weight 146.21 g/m〇l) was dissolved in 5 mi of ethyl acetate, It was then added using a syringe. The isooctyl acrylate/ethyl acetate solution was then added dropwise to the reaction solution over a period of 9 minutes. The reaction was stirred for 16 to 18 hours and the loss of NORBLOC was monitored by TLC. Once the reaction was complete, the reaction was cooled to 25 〇c. Ice-cold sterol was added to precipitate the copolymer. Two additional washes were performed to remove any unreacted monomer. The precipitate was placed under vacuum for 24 hours. The product yield was 75% (15 g) by weight. NORBLOC The mass ratio to isooctyl acrylate was 40%/60% = 2: 3. Example 13B: Preparation of UV-absorbing polymer A synthesis similar to that of Example 13A was carried out, however, the amount of reactants and solvent was too high to Approximately the amount listed in Example 13. Before adding ice-cold decyl alcohol, 200 to 400 ml of ethyl acetate solvent was removed using a rotary evaporator. 1 L of ice-cold methanol was added to precipitate the copolymer. Subsequent washing was carried out as above. 75% (150g polymer) The mass ratio of NORBLOC to isooctyl acrylate was 40%/60% = 2: 3. Example 14 Preparation of a blend of four UV-absorbing polymers in a solvent system in a separate combination. It consists of a mixture of 90% by weight of solvent and 10% by weight of two UV-absorbing polymers. The blend is prepared by dissolving two UV-absorbing polymers in a solvent system consisting of FINSOLV TN and FINSOLV TPP. The system is 98.89% FINSOLV TN and 1.11 43 201014610 % FINSOLVTPP. After dissolving the UV-absorbing polymer, the resulting solution is 89% FINSOLV TN, 1% FINS0LV TPP (which is itself a blend of 3 acid esters), and 10% A polymer that always absorbs UV. Similarly, a solution of a single polymer in a solvent system is also prepared. The choice of UV polymer and the change in mass ratio are shown in Table 9 below. Table 9 A Λ* II SPF i 1 I PFA ί ϊ I 1Κ Example 14a Hybrid 6 line 4.820 0.683 ~~ A 3320 0521 a 0.689 Example 14b PatsdSLX 3.700 0*568 — A 0.800 -0.097 — — 0216 Example 14c Example 6 90% /10% SLX 4.800 0.681 0.672 Y 3.000 0.477 0.459 Υ 0.625 Real Example 14d immso% /50%SLX 6300 0.799 0.626 Y 2200 0342 0212 Υ 0.349 Example 14e Lion column 6 60% /40% SLX 5.900 0.771 0.637 Υ 2.400 0380 0274 Υ 0.407 Example 14f imm ίο% /9〇mx 4300 0.633 0580 Υ 1.000 0.000 -0.035 Υ 0233 Example 14a Pour the 6th battle 4.820 0.683 — 3320 0.521 — — 0.689 ❹ 44 201014610

Example 14g Polyojiene ("PC") 3.000 0.477 - 1.000 0.000 - 0333 Example 14h 面面6 90% /10% PC 6.900 0.839 0.662 Y 4.000 0.602 0.469 Y 0580 Example 14i so% /50% PC 3.000 0.477 0580 N 1.900 0279 0·261 Y 0.633 Wei case 14j Side 歹丨 J 6 60% /40% PC 3.700 0.568 0.601 N 2.400 0380 0313 Y 0.649 Example 14k Example 6 10% /90% PC 2900 0.462 0.498 N 1.100 0.041 0.052 N 0.379 Array 141 Example 9.A Poly 5.900 0.771 — — 3.600 0556 — 0.610 Example 14g P〇]ya5dene (“PC”) 3.000 0.477 — — 1.000 0.000 — 0333 Example 14m Example 13A90 %/10%PC 5.500 0.740 0.741 N 3300 0*519 0501 Y 0.600 Example 14η Example 13A60 %%PC 4.500 0.653 0.653 N 2.500 0398 0334 Y 0556 Example 141 Example 13A 聚聚勿5.900 0.771 — — 3.600 0.556 — — 0.610 Example 14b Par9〇 lSLX 3.700 0.568 — — 0.800 -0.097 — — 0216 45 201014610 Example 14 〇 Example 13A90 % 10% SLX 6.740 0.829 0.751 Y 3.480 0.542 0.491 Υ 0516 Example 14ρ Implementation Example 13A60 Clear % SLX 6.100 0.785 0.690 Υ 2600 0.415 0295 Υ 0.426 Example 14q 1T Application Α 13 Α 10 % 90% SLX 6.050 0.782 0588 Υ 1300 0.114 -0.032 Υ 0215 To test the synergistic effect, use the uv absorber in the blend to polymerize The mass percentage of the matter is calculated by log SPF* and log PFA*. As previously discussed, if log φ SPF > log SPF* ' is recorded in the above table, the synergy Y is yes or N is no. A similar calculation is performed on the log PFA*. The blend of Example 6 and PARSOL SLX provided synergistic effect across the entire concentration range of both SPF and PFA traverse tests with a concentration range of 80%. The blend of Example 13A and PARSOL SLX provided synergistic effect over the full range of concentrations of both the SPF and PFA traverse tests - a concentration range of 8 %. The blend of Example 6 and POLYCRYLENE provided a synergistic PFA of only 30% across the concentration range (90 to 60), while only one specific concentration for SPF (Example 14h; 90% Example 6, 10% I&gt) ; C) Identify synergies. Example 13 A blend of A and POLYCRYLENE provided synergistic PFA for the two concentrations tested without providing synergistic effect on SPF. Example 15: Preparation of UV-absorbing monomer The acidic form of TINUVIN 213 (Ciba, Inc) was prepared as follows: 46 201014610 40.0 g TINUVIN 213 was added to a 2 L round bottom flask equipped with a stir bar and an addition funnel. Add 1 L of sterol and stir until homogenized. The yellow solution was turned into a deep amber orange by dropwise addition of 400 mL of dH20 containing 17 g of KOH through an addition funnel. The reaction was stirred for 24 hours and monitored by TLC. After the reaction was completed, about 9 mL of solvent was distilled off by rotary evaporation. 1 NHCi (aqueous solution) was added until a pH of 1 was reached by litmus paper to precipitate a white precipitate. Filter Ο

The white precipitate was washed with 1N HCl (aq.) 3×1L. It was then redissolved in 1 L of CHC13 and organic extraction was carried out in 2 X 600 mL IN HCl (aq). The organic layer was collected, dried over anhydrous Na.sub.2.sub.4, filtered, and then evaporated and evaporated. (: dried overnight under vacuum to form an acidic form of tinuvin 213 'in a yield of about 9 %. As follows, an ethylenically unsaturated UV-absorbing monomer was prepared from the acidic form of TINUVIN 213. Equipped with Freidrich condenser and mixing The rod-shaped two-neck round bottom flask was dried under vacuum and heat for 1 minute. Add 955 (0 dish m〇1) TINUVIN213 acid (prepared above), 2〇〇 rainbow diethyl puzzle, and 1.3 mL DMF. In a round bottom flask. 2 75 rainbows (〇〇37 coffee [thinthrene chloride was slowly added to the mixture. Except for a small amount of V-salt mixture until homogenization (2 to 3 hours). Add 7g of anhydrous % called, Afterwards, 18.33 g (0.141 m〇1) of methacrylic acid (hEMA) was slowly added. The reaction was carried out overnight and monitored by TLC. Once the reaction was carried out = 曰, filtered, <_, the solution was added to 1 L of separation 1

Et〇AC and 祉 祉 祉 are added to the funnel. Abandon the aqueous phase with 2靡aC1 (aqueous sputum to perform 5 X 3 有机 organic washing). Then add 2:3: 5% Na20)3 (water-soluble solution, start with the age of 47 = 1414614610 The precipitate is removed. The repeating process is carried out. Although the water-based silk is not formed, the yellow organic layer is collected and dried on anhydrous Na2S〇4, filtered and concentrated by rotary evaporation. The yellow material is redissolved in a minimum amount. The alkane was allowed to stand overnight at room temperature for recrystallization. The recrystallization was further enhanced by placing the flask in the refrigerator for up to 48 hours to form the methyl propylated form of TINUVIN 213. The yield was about 40%.Example 16: Preparation of UV-absorbing polymer The UV-absorbing polymer according to the present invention was prepared as follows: 4.0 g of TINUVIN 213-mercaptopropionate prepared as in Example 15, 5. 〇g Z -6030 calcined (available from D〇w Corning, Midland, Michigan), 1.0 g AIBN initiator, and 65 mL of ethyl acetate (EtOAc) were added to a 100 mL round bottom flask equipped with a Freidrich condenser and a stir bar. Rinse the mixture with nitrogen for 1 minute, then heat at 65 ° C under reflux 24 Then, EtOAc was evaporated by rotary evaporation, and 4.2 g of CETIOL B (dibutyl acetonate, available from Cognis Corporation, Monheim, Germany) was added to the round bottom flask to produce 70% by weight of UV absorbing polymer. 30% by weight of CETIOLB. Example 17: Preparation of UV-absorbing polymer The UV-absorbing polymer according to the invention was prepared in the same manner as in Example 16, except that 5.0 g of lauryl methacrylate was substituted for Z-6030 decane, 70 wt% UV absorbing polymer, 30 wt% CETIOLB was again produced. Example 18: Preparation of UV absorbing polymer The UV absorbing polymer according to the invention was prepared in the same manner as in Example 16, but with 5.0 g of acrylate. The octyl ester substituted Z-6030 decane again yielded 70% by weight UV absorbing polymer, 30% by weight CETIOL B. 48 201014610 Example 19: Preparation of UV absorbing monomers The acidic form of TINUVIN 109 (Ciba, Inc) was prepared as follows: Add 21.21 g of TINUVIN 109 to a 1 L round bottomed vessel equipped with a stir bar and addition funnel. Add 300 mL of ethanol and stir until homogenized. Add 1 mL of 5 wt% NaOH (water) through the addition funnel. The solution and 90 mL of deionized water were used to convert the yellow solution to a deep amber orange. The reaction was stirred for 24 hours and monitored by TLC. After the reaction was completed, the solvent was evaporated by rotary evaporation. In HC1 (aqueous solution) was added until the pH was reached by litmus paper to precipitate a white precipitate. The white precipitate was filtered and washed with 1N EtOAc (aq. Then it is re-dissolved = 500 mL CHC13 'organic with 2 X 300 mL IN HC1 (aqueous solution) = take: collect the organic layer, dry on anhydrous Na2S〇4, filter, concentrate by evaporation, and smear it Dry overnight under vacuum to form the acidic form of TINUVIN 109 at a yield of about 9%. An ethylenically unsaturated fluorene-absorbing monomer is prepared in the acidic form of TmUVIN 109 as follows. A 500 mL two-necked round bottomed vessel equipped with a Freidrich condenser and a stir bar was vacuumed and heated to dry for 1 G minutes. 678 g (0.020 m〇1) of TINUV1Nl 9 acid (prepared as described above), ruthenium 5·diethylhydrazine, and 3 mL of DMF were added to a round bottom flask. Add 2 〇 9 red (〇 〇 286 m 〇 1) sulfite gas slowly to the mixture. In addition to the small amount of Vilsmeier salt, the agitation is homogenized (2 to 3 hours). Add 7g of anhydrous,

Thereafter, 7.8 g (G.G6mQl) of methacrylic acid 2·acetic acid (HEMA) was slowly added. The anti-money night was monitored as if it had been monitored. Once the reaction was completed, the sodium carbonate was removed and the solution was added to a 1 L recording funnel. Will 5〇mL 49 201014610

EtOAc and freshly hexane were added to the funnel. By 2% post, say 々

It was allowed to stand overnight at room temperature to recrystallize. The yellow-color material is redissolved in a minimum amount of heptane' and is in |. The recrystallization was further enhanced by placing the flask in the refrigerator for up to 48 hours to form a thiol-acrylated form of TINUvin ι〇9 in a yield of about 40% and a melting point of about 42t:. Example 20: Preparation of UV Absorbing Polymer The UV absorbing polymer according to the present invention was prepared as follows: 4.0 g of TINUVIN 109 methacrylate prepared as in Example 19, 5.0 g of Z_6030 simmered (available from Midland 'Michigan Dow) Corning), 〇g AIBN initiator, and 65 mL of ethyl acetate (EtOAc) were added to a 100 mL round bottom flask equipped with a Freidrich condenser and a stir bar. The mixture was flushed with nitrogen for 1 Torr and then heated under reflux at 65 °C for 24 hours. Then, EtOAc was distilled off by rotary evaporation, and 4.2 g of CETIOL B (dibutyl acetonate, available from Cognis Corporation, Monheim, Germany) was added to a round bottom flask to give 70% by weight of UV absorbing polymer, 30 parts by weight. %CETIOLB. [40%TINUVIN 109, 50% decane, 10% initiator] Example 21: Preparation of UV-absorbing polymer The UV-absorbing polymer according to the invention was prepared in the same manner as in Example 20, but with 5.0 g of methacrylic acid. Lauryl ester substituted Z-6030 decane' again produced 70% by weight of UV absorbing polymer, 30% by weight CETIOLB ° 50 201014610 Example 22: Preparation of UV absorbing polymer Prepared in the same manner as in Example 20 UV absorption according to the invention The polymer, but replacing Z-6030 decane with 5.0 g of isooctyl acrylate, again produced 70% by weight of UV absorbing polymer, 30% by weight of CETIOLB. Example 23: UV Absorption - Comparing UV-absorbing polymers having different UV-absorbing chromophores The UV-absorbing polymer of Example 20 and the UV-absorbing polymer of Example 6 were separately dissolved in CETIOLB, each to The concentration was 20% by weight. Since each polymer contained 40% by weight of UV-absorbing chromophore, each sample contained 8% by weight (20% X 40%) of chromophore. An in vitro sun protection test method was performed on both materials to compare the ability of each pair to absorb UV radiation. The results are shown in Table 10 below: _Table 10_

SPF PFA in solution in polymer CETIOLB__Polymer % chromophore %_ Example 20 20 8 11.59 9.43 Example 6 20 8 12.49 5.01 The results indicate that when tested in CETIOLB, the polymer compared to Example 6 (It has NORBLOC as a UV-absorbing moiety), and the polymer of Example 20, which contains TINUVIN 109 as a UV-absorbing chromophore, has excellent UV-A absorption properties. The PFA/SPF ratio of the polymer of Example 20 was 0.89, while the polymer of Example 6 had a PFA/SPF ratio of only 0.40. This recommendation achieves even higher levels of UV-A protection by selecting TINUVIN 109 as the UV absorbing part. Furthermore, its recommendation by selecting 51 201014610 TINUVIN 109 should be able to meet the desired minimum PFA/SPF ratio (0.33) while still achieving a high SPF. Example 24 A composition comprising a UV absorbing polymer was prepared. The composition consists of the ingredients shown in Table 11 below: Table 11 Trade name INCI or CTFA name percentage Water-----· 59.3 Pemulen TR 1 Acrylic acid S/Acrylic CiZ-3 ◦ vinegar Crosslinked polymer 0.2 SPECTRAGARD octane diol, hexanediol, decyl isodecyl ketone 0.6 ARLACEL 165 glyceryl stearate, PEG-100 stearate 1.7 AMPHISOL K whale 蠛 _ potassium acetate 0.7 Example 20 polymer UV-absorbing polymer 20.0 CETIOL B dibutyl adipate 6.0 FINSOLV TN benzyl acid clrc15 alkyl ester 3.0 MYGLIOL 812 caprylic/capric acid triglyceride 7.0 LANETTE 16 cetyl alcohol 0.5 COSMEDIA ATH sodium polyacrylate and Ethylhexyl stearate and ten 1.0 Trideceth-6 A total of 100 PEMULEN TR 1 is available from N〇ve〇n Inc. of Cleveland, Ohio. 52 201014610 ARLACEL 165 is available from Uniqema Inc. of Chicago, Illinois. AMPHISOL K is available from Parsippany, DSM Nutritional Products, New Jersey. CETIOL B and LANETTE 16 are available from Cognis Care Chemicals, Monheim, Germany. FINSOLV TN is available from Elmwood Park, Finetex Inc. of New Jersey. MYGLIOL 812 is available from Witten's Sasol Germany GmbH, Germany. SPECTRAGARD is available from Philadelphia, Inolex Chemical, Pennsylvania

The composition of Example 24 was prepared by first mixing an aqueous phase with PEMULEN and heating to 85 °C. A small amount of sodium hydroxide was added to neutralize PEMULEN to a pH of 5.5 to 6.0. The oil phase was then prepared by mixing the remainder of the ingredients (except COSMEDIA ATH and SPECTRAGARD), adding it to the aqueous phase and homogenizing the two phases for 5 minutes using a mixer set at 3500 rpm. Then slowly add COSMEDIA ATH to cool the mixture to 30 °C. Then add SPECTRAGARD, mix gently, and cool to room temperature. The composition of Example 24 exhibited excellent spreadability and aesthetics. It is to be understood that the foregoing description of the invention is intended to be illustrative and not restrictive Other aspects, advantages, and modifications are within the scope of the patent application. BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 shows the absorbance spectra of the UV-absorbing polymers of Examples 5 and 6 and the homopolymer of Example 8. 53

Claims (1)

201014610 VII. Patent application scope: 1. A UV-absorbing polymer with the following chemical structure. R I --ch2-C Wherein 仏 is the first suspension group comprising UV-absorbing triple saliva; Han 2 is the second release group comprising: a) 1 to about 50 siloxane linkages, b) having 7 to 16 carbon ❹ atoms saturated or An unsaturated hydrocarbon moiety, or c) a combination thereof, a moiety having no absorption of r2; each R' is independently 11 or (:1 to <:;:12 alkyl; 11 is 1 to 6〇〇〇; m is 2 to 6300; The UV absorbing polymer has a weight average molecular weight of at least about 2000 and comprises at least about 5 moles. 2. A uv-absorbing polymer according to claim 1 wherein R is 3. The uv-absorbing polymer of item 1, wherein η is from about 2 to about 3500. 4. The UV-absorbing polymer of claim 1, wherein m is from about 3 to about 4,000. The absorbed polymer of item 1 having a weight average molecular weight of from about 2,000 to about 1,000,000. 6. The UV absorbing polymer of claim 1 has a center comprising a UV absorbing portion having the formula: I) 54 201014610 Wherein each r14 is independently selected from the group consisting of hydrogen, crc2G alkyl, alkoxy, fluorenyl, alkyloxy, alkylamino, and halogen; each R15 and Κ22 are independently selected from nitrogen a group consisting of a C1-C20 alkyl group, an alkoxy group, a aryl group, a decyloxy group, and an alkylamine group, at least one of R15 and R22 is not nitrogen; and R_21 is selected from a C1-C2G alkyl group, and is sintered. Oxyl, aryl, alkyloxy, and amphoteric amine. 7. The UV absorbing polymer of claim 6 wherein R14 is a halogen. 8. The UV-absorbing polymer according to claim 6, wherein the UV-absorbing triazole is a compound of the formula I, wherein R14 is halogen, R15 is butyl, and R21 is -ch2ch2co2c8h17 〇55 201014610 9. Scope of application The UV-absorbing polymer of item 1, which has no free fraction. 10. The UV absorbing polymer of claim 1, wherein the R2 is derived from monodecyl propyleneoxy propyl polydecyl decane (mPDMS). 11. The UV absorbing polymer of claim 1 wherein the 112 series is derived from decyl propylene oxy propylene tridecyl decane (Z-6030). 12. The UV-absorbing polymer of claim 1 wherein the center is 2-(2'-hydroxy-5'-methacryloxyethylphenyl)-2H-benzotriazole. 13. An aqueous composition comprising: a UV absorbing polymer having the following chemical formula: R· ... 1 R · ... I wri2 wc = o wl * 2 w I c = 1 0 I 0 1 I R1 ή r2 wherein the first pendant group comprises a UV-absorbing moiety; and R2 is a second suspension group comprising: a) at least one siloxane coupling, b) having 7 to 16 carbon atoms saturated or unsaturated a hydrocarbon moiety, or c) a combination thereof; each R' is independently Η or C 到 to C12 alkyl; η is from 1 to 6000; m is from 2 to 6300; the UV absorbing polymer has a weight average molecular weight of at least about 2,000 and includes At least about 5 moles. 14. The aqueous composition of claim 13, wherein the UV absorbing polymer has no free portion. 15. The aqueous composition of claim 13, wherein the polymer that absorbs UV 56 201014610 has a water solubility of less than about 3% by weight. 16. The aqueous composition of claim 13, wherein the UV absorbing polymer has a weight average molecular weight of from about 2,000 to about 1,000,000. 17. The aqueous composition of claim π, wherein the UV absorbing polymer comprises from about 1 Torr to about 9 Torr. 18. The aqueous composition of claim 13 of the patent scope, wherein the center comprises a portion that absorbs UV-A. ❹I9. The aqueous composition of claim 13, wherein R1 comprises a di-sigma sitting that absorbs U V . 20. The aqueous composition of claim 13 of the scope of the patent application, wherein the 仏 does not absorb the U V portion. 21. The aqueous composition of claim 13, wherein the R2 is derived from monomethacryl decyl propyl polydimethyl decane (mPDMS). 22. The aqueous composition of claim 13, wherein the R2 is derived from methyl propyloxy bis-trimethoxy zephyr (Z-6030). ❹ 23. The aqueous composition of claim 13, wherein the towel & is 2 (2,-hydroxy-5-methacryloxyethylphenyl)_2H•benzotriazole. 24. The aqueous composition of claim 13, which comprises from about 0.5% by weight to about 80% by weight of the uv-absorbing polymer. 25. The aqueous composition of claim 13 further comprising a cosmetically acceptable topical carrier. 26. The aqueous composition of claim 13 further comprising a second UV absorbing polymer. 27. The aqueous composition of claim 26, wherein the second absorption 57 201014610 UV polymer comprises a UV-B absorbing portion. 28. The aqueous composition of claim 13 further comprising a solvent system comprising a solvent having a dielectric constant of from about 3 to about 8. 29. A method of protecting mammalian skin or hair from UV radiation, comprising applying to said skin or hair an aqueous composition as in claim 13 of the patent application. 30. A blend comprising: a first UV absorbing polymer comprising a UV-A absorbing portion; and a second UV absorbing polymer comprising a UV absorbing portion; wherein the blend is capable of providing an increase Both the SPF and the synergistic PFA protect at least about 40% by mass of the first and second UV absorbing polymers. 31. The blend of claim 30, wherein the first UV absorbing polymer comprises a carbon chain backbone. 32. The blend of claim 30, wherein the first UV absorbing polymer comprises a carbon chain backbone and the second UV absorbing polymer comprises a siloxane backbone. 33. The blend of claim 30, wherein the first UV absorbing polymer is a compound having the formula: R_ 1 R · I 1 C = 0 C = 1 0 II 0 I 1 Ri η I r2 — 58 201014610 wherein R! is a first suspension group comprising a UV absorbing moiety; and R2 is a second suspension group comprising: a) at least one siloxane coupling, b) a hydrocarbon moiety having 7 to 16 carbon atoms, Or c) a combination thereof; each R' is independently Η or C! to C12 alkyl; η is from 1 to 6000; m is from 2 to 6300; the UV absorbing polymer has a weight average molecular weight of at least about 2000 and includes at least about 5 Moer % Ri. 34. The blend of claim 30, wherein the first UV absorbing polymer has a weight average molecular weight of at least about 2000 to about 1,000,000. 35. The blend of claim 30, wherein the second UV absorbing polymer has a weight average molecular weight of at least about 2,000. 36. The blend of claim 30, wherein the first UV absorbing polymer has a weight average molecular weight of at least about 50,000 to about 500,000, and the second UV absorbing polymer has a weight average molecular weight of at least about 5,000. 37. The blend of claim 30, further comprising a solvent that promotes synergism. 38. The blend of claim 30, further comprising a benzyl ester. 39. The blend of claim 30, wherein the portion that absorbs UV-A comprises a UV-absorbing triazole. 40. The blend of claim 30, wherein the second UV-B absorbing portion comprises benzylidene malonic acid vinegar. 41. The blend of claim 30, further comprising a solvent system comprising a solvent having a dielectric constant of from about 3 to about 8. 59