US2614940A - Ultraviolet light absorbing film - Google Patents

Ultraviolet light absorbing film Download PDF

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Publication number
US2614940A
US2614940A US68624A US6862448A US2614940A US 2614940 A US2614940 A US 2614940A US 68624 A US68624 A US 68624A US 6862448 A US6862448 A US 6862448A US 2614940 A US2614940 A US 2614940A
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Prior art keywords
film
ultraviolet light
light absorbing
absorbing film
salt
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Expired - Lifetime
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US68624A
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Harlan B Freyermuth
William O Ney
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GAF Chemicals Corp
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General Aniline and Film Corp
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Priority to US68624A priority Critical patent/US2614940A/en
Priority to FR1002886D priority patent/FR1002886A/en
Priority to DEG694A priority patent/DE860271C/en
Priority to BE492985A priority patent/BE492985A/en
Priority to GB33132/49A priority patent/GB671857A/en
Priority to CH289699D priority patent/CH289699A/en
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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
    • 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
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/35—Ketones, e.g. benzophenone
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C67/00—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/41—Compounds containing sulfur bound to oxygen
    • C08K5/42—Sulfonic acids; Derivatives thereof
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
    • G03C1/815—Photosensitive materials characterised by the base or auxiliary layers characterised by means for filtering or absorbing ultraviolet light, e.g. optical bleaching
    • G03C1/8155—Organic compounds therefor

Definitions

  • This invention relates to ultraviolet light absorbing films. 7
  • plastic materials of both the water-soluble and water insoluble type such as gelatin, polyvinyl alcohol, cellulose acetate and the like become colored, usually yellowing, and sometimes brittle and many eventually deteriorate upon exposure to sunlight.
  • the present invention is concerned with ultraviolet light absorbers for the water soluble film forming materials which may be used themselves in packaging, as for example cellophane, or which may be used as a coating upon other materials which fade or deteriorate insunlight.
  • the absorption of ultraviolet light in materials such as cellophane is particularlyimportant because of the wide spread usesof cellophane as a packaging material, allowing fading or deterioration of the goods which the package contains.
  • the absorber should be capable of absorbing substantially all of; the ultraviolet light within the Wave length range 200 to 400 millimicrons and even into'the visible range as high as 4.40 millimicrons.
  • a film is cast from a water solution of a water soluble film forming plastic containing a compound having the following general structure:
  • one B is hydrogen and the other R is an alkaline sulphonate radical.
  • the sulphonic acid is neutralized with any of various alkaline material including alkaline earth metals, ammonia, amines such as aliphatic, aromatic, cycloparafiinic and heterooyclic amines, and preferable alkali metals, alkali hydroxides,10r alkaline alkali metal salts (e. g. NazCOal.
  • alkaline earth metals ammonia
  • amines such as aliphatic, aromatic, cycloparafiinic and heterooyclic amines
  • alkali metals alkali hydroxides,10r alkaline alkali metal salts (e. g. NazCOal.
  • alkali hydroxides alkali hydroxides
  • 10r alkaline alkali metal salts e. g. NazCOal.
  • 'It is an important element of the present in;- vention that the compound have a pH in the range of 5 to 9.5.
  • the above compound, for example, in acid form has a pH of about 1.5
  • Example 2 Ten parts of the sulphonic acid product of Example 1 was dissolved by heating in parts like.
  • Example 1 To 90 parts of a 10% aqueoussolution of gela-'- tin was added 1.0 part of the sodium' salt of 2,4-dihydroxybenzophenone-5-su1fonic acid. AA film resembling thatthe Example 1 was obtained.
  • the film of' the present invention may be a self-supported film such as the cellophane used in packaging or it may be used as a protective coating on other bases such as water soluble or water insoluble plastic materialsas, for example, photographic cellulose acetate film, glass or the
  • the compounds of the present invention are cclorlessandj s such absorb very little visible .lig ht-and subsequently do not distort thecolor balance of articles which they may protect. They are useful in photographic .filters sun tan lotions, vand cellophane potato chippackages, .among other uses. 3 Y
  • the compound ofExample 1 contains :the sul- -Ionic acid group in the substituted :tresorcinol) ring-because onloxidation, benzoic .acid is isolated from the reaction products, which demonstrates that sulfonation doe-snot take place in the other ring.
  • Examples of “film-forming "organic plastic mater-ials which are soluble in the aqueousmed'iums "hereinemp'loyed,-that is aqueous mediums h-aving -a pH in the range-o-f 5 to 9;5 include regencellulose,- partially hydrolyzed polyvinyl "acetate, polyvinyl alcohol, elatin, carboxymethyl' cellulose, hydroxyxn'thyl cellulose, urea-formaldehy'de resins, melamine iormaldhyde resins,
  • the material absorbs substantially all of the light below :the visual range whileritself being colorless .or veryipale yellow.
  • An 'improvedultraviolet light absorbing film comprising a film-forming plastic soluble in an aqueous medium having a pH of 5 to 9.5 and a salt :of a .sul-fonic :acid, which sulfonic acid has the formula: v

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  • Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Veterinary Medicine (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Physics & Mathematics (AREA)
  • Birds (AREA)
  • Emergency Medicine (AREA)
  • Materials Engineering (AREA)
  • Epidemiology (AREA)
  • General Physics & Mathematics (AREA)
  • Dermatology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)

Description

Och 1952 H. B. FREYERMUTH ETAL 2,514,940
I ULTRAVIOLET LIGHT ABSQRBING FILM Filed Dec. 31, 1948 so I 0.|
7o Guryes showing the relationship of castlng pH to transmission for falls of 2,4;dlhydroxybpnzophenone-5- sulfomc acld sodlum salt 0.2 so
Concentration I092, in Poly Vinyl Alcohol ,3- (D 5 Thickness O.l mm g 50 2 0.3
iu .2 g i a g pH=5.0 pH=9.45 0. 4o 0.4
I 0.6 20 or! 0.9 l0 L0 j L5 0 J 2.0 220 260 300 340 380 400 420-440 460 500 Wavelength in Millimicrons INVENTOR William 0. Ney
BY Harlan B. Freyermuth Patented Oct. 21, 1952 Harlan B. Freyermuth and William 0. Ney, Easton, Pa assignors to General Aniline & Film Corporation, New York, N. Y., a corporation of Delaware Application December a1, 1948, Serial No. 68,624
8 Claims. (01. 106-125) This invention relates to ultraviolet light absorbing films. 7
It is well known that colored objects such as dyed textiles and the like fade when exposed for prolonged periods to the effect of sunlight. Plastic materials of both the water-soluble and water insoluble type such as gelatin, polyvinyl alcohol, cellulose acetate and the like become colored, usually yellowing, and sometimes brittle and many eventually deteriorate upon exposure to sunlight. The present invention is concerned with ultraviolet light absorbers for the water soluble film forming materials which may be used themselves in packaging, as for example cellophane, or which may be used as a coating upon other materials which fade or deteriorate insunlight. The absorption of ultraviolet light in materials such as cellophane is particularlyimportant because of the wide spread usesof cellophane as a packaging material, allowing fading or deterioration of the goods which the package contains.
To be most effective, the absorber should be capable of absorbing substantially all of; the ultraviolet light within the Wave length range 200 to 400 millimicrons and even into'the visible range as high as 4.40 millimicrons.
It is a further object of the present invention to provide a film cast from a water solution of a water soluble film forming plastic containing a Water soluble compound particularly adapted to absorbing light having a Wave length above about 400 millimicrons.
These and other objects are attained by the present invention wherein a film is cast from a water solution of a water soluble film forming plastic containing a compound having the following general structure:
OHv
wherein one B is hydrogen and the other R is an alkaline sulphonate radical.
We have discovered that these compounds when combined with a water soluble plastic in acqueous solution having a pH in the range to 9.5 are unexpectedly compatable and do not crystallize out or make an opaque film as might be expected but rather form a clear film which has the desired light absorption.
The sulphonic acid is neutralized with any of various alkaline material including alkaline earth metals, ammonia, amines such as aliphatic, aromatic, cycloparafiinic and heterooyclic amines, and preferable alkali metals, alkali hydroxides,10r alkaline alkali metal salts (e. g. NazCOal. The'following compounds are illustrative:
and preferably:
'It is an important element of the present in;- vention that the compound have a pH in the range of 5 to 9.5. The above compound, for example, in acid form has a pH of about 1.5
a and is unstable and absorbs very-littlei light above 390 millimicrons. v
The following examples will serve to illustrate the invention and are preferred embodiments thereof, but are not intended to limit the 'invention. EwampleI 43 parts of 2,4-dihyd ox benzophenone was added to 200 parts of 29% oleum at a temperature of about 1520 C. and allowed to stand for about hr. The mixture was added to 1,500 parts of ice whereupon the sulfonated product began to separate out. The mixturewas then re dissolved by heating 'to 35 C. and stirred with 5, parts 'Nuchar and15 parts filter cell (commercial clarifying agents). After filtering, 1000 parts, of, a saturated sodium carbonate solution was added. The sodium salt, of 2,4-dihydrox-yv .benzophenone -.5 sulphonic acid precipitated,
Example 2 Ten parts of the sulphonic acid product of Example 1 was dissolved by heating in parts like.
of water to 80-90 C. To this solution was added an equiyalent amount of an aqueous solution of cyclohexyl amine. On cooling, the cyclohexyl amine salt of 2,4-dihydroxybenzophenone precipitated as large, nearlycolorless plates (pH of acteristic of absorbing light .in the ran e 2 20 7 to 430 millimicrons.
To 90 parts of a 10% aqueoussolution of gela-'- tin was added 1.0 part of the sodium' salt of 2,4-dihydroxybenzophenone-5-su1fonic acid. AA film resembling thatthe Example 1 was obtained.
Example 4 T0730 ;parts .of af1I0%" solution of gelatin. was
aiided-1.0. part-of-cyclohexyl amine-salt of' 2,4-
dihy'drQXybe ZQDhenone-S-sulfonic .acid. A film resembling that of .iExample ".2 was obtained. The graph shown in the drawing'i's self-explanatory. It-demonstrates that the compounds of the present invention absorbsubstantially all of the ultraviolet light without extending substantially into the visible range and shows the 'efiect of the pH o'nthe absorption characteristics of these compounds. I p
The film of' the present invention may be a self-supported film such as the cellophane used in packaging or it may be used as a protective coating on other bases such as water soluble or water insoluble plastic materialsas, for example, photographic cellulose acetate film, glass or the The compounds of the present invention are cclorlessandj s such absorb very little visible .lig ht-and subsequently do not distort thecolor balance of articles which they may protect. They are useful in photographic .filters sun tan lotions, vand cellophane potato chippackages, .among other uses. 3 Y
The compound ofExample 1 contains :the sul- -Ionic acid group in the substituted :tresorcinol) ring-because onloxidation, benzoic .acid is isolated from the reaction products, which demonstrates that sulfonation doe-snot take place in the other ring.
' Examples of "film-forming "organic plastic mater-ials which are soluble in the aqueousmed'iums "hereinemp'loyed,-that is aqueous mediums h-aving -a pH in the range-o-f 5 to 9;5 include regencellulose,- partially hydrolyzed polyvinyl "acetate, polyvinyl alcohol, elatin, carboxymethyl' cellulose, hydroxyxn'thyl cellulose, urea-formaldehy'de resins, melamine iormaldhyde resins,
polyvinyl-methyl ether, eta: I Cont'rol-of the pl-Iof thecompound'orthe pr es- [file of this patent:
ent invention to keep it in the range pH 5 to 9.5
is important for substantial absorption to 400 to 440 millimicrons and the pH within those limits is substantially proportional to the Wave length of light absorbed within the range, indicated. Thus the material absorbs substantially all of the light below :the visual range whileritself being colorless .or veryipale yellow.
It will be understood that the amount of these compounds used will depend upon the thickness of the supporting film and the pH. In general the higher the pH-and the larger the amount of compound the more the curves will extend toward the :visible range. At a pH of 5.0 for example,
pound per cm; gives satisfactory absorption.
We claim: '1. An 'improvedultraviolet light absorbing film comprising a film-forming plastic soluble in an aqueous medium having a pH of 5 to 9.5 and a salt :of a .sul-fonic :acid, which sulfonic acid has the formula: v
wherein orient the radicalsR ,andiR" 'isfhydrovgenand the otheri-s ISOa'H, said salt having am in aqueous .solutionilinthe range "5 to 925.
2. The film of claim .1 .wherein'R 'is'hydrogeli, RCisan orithoesOs'H radical in the mated-struc- .tural liormula, and the .salt a .sodiumsalt.
3.. The'film of claimil wherein R ishydrogen, .Ris an SOaH.radica1 in the..5 position ,inthe recited structural .formula, and the salt isla sodium salt. Q I
4. The .of claim ,1 wherein ,the said .film- [forming plastic is regenerated cellulose. 1
5. The film of claim 1 wherein the said fihnforming plastic .is polyvinylalcohol. Y
.6. The film-of .c-laiml wherein the said .film- -f.orming.plasticis gelatine. 7 r 1 v 7.. .The filmof .cl aim v1 wherein .thesaid filinforming plastic .is .a -partially hydrolyzedpoly- .vinylacetate. v I
8.. ,The film of claiml wherein thesaid-film- .ifonning .plastic vis hydroxymethyl cellulose.
WILLIAMOMNEKN-L REFERENCES CITED The following references are of lti'ecord in nthe UNITED STATES-PATENTS Number Name 7 Date 2,069,773 Reid Feb. 9, 1937 2,099,441 Heckert Nov. 16,1937 2,199,927 Underwood May 7, 1940 2,434,496 Houtman 1 Jan. 13, 1948

Claims (1)

1. AN IMPROVED ULTRAVIOLET LIGHT ABSORBING FILM COMPRISING A FILM-FORMING PLASTIC SOLUBLE IN AN AQUEOUS MEDIUM HAVING A PH OF 5 TO 9.5 AND A SALT OF A SULFONIC ACID, WHICH SULFONIC ACID HAS THE FORMULA:
US68624A 1948-12-31 1948-12-31 Ultraviolet light absorbing film Expired - Lifetime US2614940A (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
US68624A US2614940A (en) 1948-12-31 1948-12-31 Ultraviolet light absorbing film
FR1002886D FR1002886A (en) 1948-12-31 1949-12-20 Ultraviolet light absorbing film
DEG694A DE860271C (en) 1948-12-31 1949-12-27 Process for the production of ultraviolet light absorbing films
BE492985A BE492985A (en) 1948-12-31 1949-12-28 Ultraviolet light absorbing film
GB33132/49A GB671857A (en) 1948-12-31 1949-12-28 Ultraviolet light absorbing film
CH289699D CH289699A (en) 1948-12-31 1949-12-31 Solution intended for the formation of films absorbing ultraviolet light and method for the preparation of this solution.

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US68624A US2614940A (en) 1948-12-31 1948-12-31 Ultraviolet light absorbing film

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GB (1) GB671857A (en)

Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2748021A (en) * 1953-06-24 1956-05-29 Eastman Kodak Co Solubilized benzal derivatives of alpha-methyl-alpha-phenyl hydrazines and ultraviolet radiation absorbing products thereof
DE1002625B (en) * 1952-10-31 1957-02-14 Eastman Kodak Co Photographic material protected from the action of ultraviolet radiation
DE958526C (en) * 1952-10-31 1957-02-21 Eastman Kodak Co Photographic material protected from the action of ultraviolet radiation and having an ultraviolet absorbing layer
DE964654C (en) * 1952-10-31 1957-05-23 Eastman Kodak Co Photographic material having an ultraviolet absorbing layer
US2876210A (en) * 1954-02-10 1959-03-03 Gen Aniline & Film Corp 2,2'-dihydroxy-4, 4'-substituted benzophenones as ultraviolet absorbents for gr-a rubber
US2888315A (en) * 1956-01-24 1959-05-26 Joseph E Moore Process for preventing yellowing of wool
US2944912A (en) * 1958-07-31 1960-07-12 Printing Arts Res Lab Inc Ultraviolet absorbing watercolor paint compositions
US2983604A (en) * 1955-11-03 1961-05-09 Gen Aniline & Film Corp Quenching solution for fluorescent photographic paper employed in the manufacture ofhalftone negatives
US2989416A (en) * 1958-01-06 1961-06-20 Du Pont Werner complexes of orthohydroxyl substituted benzophenone
US3043709A (en) * 1957-08-01 1962-07-10 Du Pont Organic polymeric structure having an ultraviolet light absorbent compound incorporated therein
US3076723A (en) * 1958-05-26 1963-02-05 Du Pont Coating weight determination by means of ultraviolet light
US3124584A (en) * 1964-03-10 Process for the production of hetero-
US3160665A (en) * 1957-03-06 1964-12-08 Ciba Ltd Hydroxy-benzophenones
US3214463A (en) * 1960-05-12 1965-10-26 Du Pont Uv-absorbing sulfonated benzophenone derivatives
US3247127A (en) * 1960-04-14 1966-04-19 Eastman Kodak Co Light-absorbing water-permeable colloid layer containing an oxonol dye
US3506758A (en) * 1964-03-10 1970-04-14 Colgate Palmolive Co Substantive sunscreening compositions
US3670074A (en) * 1971-01-22 1972-06-13 Cyril Doner Sunscreen formulation containing triethanolamine neutralized 2-hydroxy-4-methoxy-benzophenone-5-sulfonic acid
US3867302A (en) * 1971-12-24 1975-02-18 Sinloihi Co Ltd Organic phosphors and process for production thereof
US4840788A (en) * 1986-07-15 1989-06-20 Ici Americas Inc. Nonalcoholic sunscreen gel

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5275810A (en) * 1988-02-25 1994-01-04 L'oreal Cosmetic composition for maintaining the hairstyle containing an oxazoline polymer and a 2-hydroxy-4-methoxy-benzophenone-5-sulphonic acid, salified or otherwise
LU87142A1 (en) * 1988-02-25 1989-09-20 Oreal Societe Anonyme Francais COSMETIC COMPOSITION FOR HOLDING HAIRDRESSING CONTAINING OXAZOLINE POLYMER AND 2-HYDROXY 4-METHOXY BENZOPHENONE 5-SULFONIC ACID

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2069773A (en) * 1934-09-15 1937-02-09 Du Pont Delustered cellulosic product and method of preparing same
US2099441A (en) * 1934-09-15 1937-11-16 Du Pont Cellulosic product and method for preparing same
US2199927A (en) * 1937-03-17 1940-05-07 Du Pont Cellulosic pellicle
US2434496A (en) * 1945-03-02 1948-01-13 Dow Chemical Co Light stable compositions comprising polymeric vinylidene chloride or vinyl chloride and certain 5-substituted 2-hydroxybenzophenones

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE640908C (en) * 1933-03-12 1937-01-15 I G Farbenindustrie Akt Ges Colorless or lightly colored protective cover for light or air-sensitive goods of all kinds

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2069773A (en) * 1934-09-15 1937-02-09 Du Pont Delustered cellulosic product and method of preparing same
US2099441A (en) * 1934-09-15 1937-11-16 Du Pont Cellulosic product and method for preparing same
US2199927A (en) * 1937-03-17 1940-05-07 Du Pont Cellulosic pellicle
US2434496A (en) * 1945-03-02 1948-01-13 Dow Chemical Co Light stable compositions comprising polymeric vinylidene chloride or vinyl chloride and certain 5-substituted 2-hydroxybenzophenones

Cited By (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3124584A (en) * 1964-03-10 Process for the production of hetero-
DE1002625B (en) * 1952-10-31 1957-02-14 Eastman Kodak Co Photographic material protected from the action of ultraviolet radiation
DE958526C (en) * 1952-10-31 1957-02-21 Eastman Kodak Co Photographic material protected from the action of ultraviolet radiation and having an ultraviolet absorbing layer
DE964654C (en) * 1952-10-31 1957-05-23 Eastman Kodak Co Photographic material having an ultraviolet absorbing layer
DE969374C (en) * 1952-10-31 1958-05-22 Eastman Kodak Co Photographic material protected from the action of ultraviolet radiation with an ultraviolet absorbing layer
US2748021A (en) * 1953-06-24 1956-05-29 Eastman Kodak Co Solubilized benzal derivatives of alpha-methyl-alpha-phenyl hydrazines and ultraviolet radiation absorbing products thereof
US2876210A (en) * 1954-02-10 1959-03-03 Gen Aniline & Film Corp 2,2'-dihydroxy-4, 4'-substituted benzophenones as ultraviolet absorbents for gr-a rubber
US2983604A (en) * 1955-11-03 1961-05-09 Gen Aniline & Film Corp Quenching solution for fluorescent photographic paper employed in the manufacture ofhalftone negatives
US2888315A (en) * 1956-01-24 1959-05-26 Joseph E Moore Process for preventing yellowing of wool
US3160665A (en) * 1957-03-06 1964-12-08 Ciba Ltd Hydroxy-benzophenones
US3043709A (en) * 1957-08-01 1962-07-10 Du Pont Organic polymeric structure having an ultraviolet light absorbent compound incorporated therein
US2989416A (en) * 1958-01-06 1961-06-20 Du Pont Werner complexes of orthohydroxyl substituted benzophenone
US3076723A (en) * 1958-05-26 1963-02-05 Du Pont Coating weight determination by means of ultraviolet light
US2944912A (en) * 1958-07-31 1960-07-12 Printing Arts Res Lab Inc Ultraviolet absorbing watercolor paint compositions
US3247127A (en) * 1960-04-14 1966-04-19 Eastman Kodak Co Light-absorbing water-permeable colloid layer containing an oxonol dye
US3214463A (en) * 1960-05-12 1965-10-26 Du Pont Uv-absorbing sulfonated benzophenone derivatives
US3506758A (en) * 1964-03-10 1970-04-14 Colgate Palmolive Co Substantive sunscreening compositions
US3670074A (en) * 1971-01-22 1972-06-13 Cyril Doner Sunscreen formulation containing triethanolamine neutralized 2-hydroxy-4-methoxy-benzophenone-5-sulfonic acid
US3867302A (en) * 1971-12-24 1975-02-18 Sinloihi Co Ltd Organic phosphors and process for production thereof
US4840788A (en) * 1986-07-15 1989-06-20 Ici Americas Inc. Nonalcoholic sunscreen gel

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GB671857A (en) 1952-05-14
CH289699A (en) 1953-03-31
FR1002886A (en) 1952-03-11
DE860271C (en) 1952-12-18
BE492985A (en) 1950-01-14

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