US3171784A - Copolymer of vinyl pyrrolidone and vinyl acetate as aerosol hair spray - Google Patents

Copolymer of vinyl pyrrolidone and vinyl acetate as aerosol hair spray Download PDF

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Publication number
US3171784A
US3171784A US621206A US62120656A US3171784A US 3171784 A US3171784 A US 3171784A US 621206 A US621206 A US 621206A US 62120656 A US62120656 A US 62120656A US 3171784 A US3171784 A US 3171784A
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Prior art keywords
vinyl
hair
copolymer
aerosol
grams
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Expired - Lifetime
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US621206A
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English (en)
Inventor
Daniel B Witwer
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GAF Chemicals Corp
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General Aniline and Film Corp
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Application filed by General Aniline and Film Corp filed Critical General Aniline and Film Corp
Priority to US621206A priority Critical patent/US3171784A/en
Priority to GB31305/57A priority patent/GB828970A/en
Priority to FR1187884D priority patent/FR1187884A/fr
Priority to DEG23320A priority patent/DE1089930B/de
Priority claimed from US816054A external-priority patent/US3014898A/en
Priority to FR828237A priority patent/FR1265403A/fr
Priority to DES68680A priority patent/DE1129682B/de
Priority to BE591236D priority patent/BE591236A/xx
Priority to GB18465/60A priority patent/GB878970A/en
Publication of US3171784A publication Critical patent/US3171784A/en
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Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/06—Preparations for styling the hair, e.g. by temporary shaping or colouring
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • A61K8/817—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Compositions or derivatives of such polymers, e.g. vinylimidazol, vinylcaprolactame, allylamines (Polyquaternium 6)
    • A61K8/8182—Copolymers of vinyl-pyrrolidones. Compositions of derivatives of such polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B15/00—Pretreatment of the material to be shaped, not covered by groups B29B7/00 - B29B13/00
    • B29B15/02—Pretreatment of the material to be shaped, not covered by groups B29B7/00 - B29B13/00 of crude rubber, gutta-percha, or similar substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
    • C08C3/00—Treatment of coagulated rubber
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S424/00—Drug, bio-affecting and body treating compositions
    • Y10S424/01—Aerosol hair preparation
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S424/00—Drug, bio-affecting and body treating compositions
    • Y10S424/02—Resin hair settings

Definitions

  • the present invention relates to aerosol film forming compositions and particularly to improved hair waving and setting compositions.
  • the film or coating becomes tacky and develops a greasy feel.
  • some derivatives have the tendency of rubbing loose and falling off the hair in the form of small flakes resembling dandruff, while others require alkaline media for easy removal from the hair. It is well recognized among hair stylists and beauticians that ammonia has distinct hair stiffening characteristics whereby the fibers of the hair are attacked with a subsequent altering of its natural life.
  • shellac Alcoholic solutions of shellac have also been employed and are currently sold in limited amounts in a Freon System.
  • alkaline media such as caustic soda or caustic potash for preparation of the solution prior to formulation in a pressurized can.
  • alkaline media must be employed to remove it from the hair.
  • the moisture pickup is approximately one-third of the relative humidity and therefore the resulting film contains about 17% moisture.
  • detackifying agents such as shellac, cellulose acetate-propionate, etc.
  • the former yields films which become opaque at high humidities, and the latter yields a film insoluble in ethyl alcohol.
  • Carboxy-methylcellulose, cellulose acetate, methyl methacrylate polymer, polyvinyl formal, etc. are not effective as detackifiers under conditions of extremely high humidities.
  • composition possessing new and desirable properties for application to human hair comprises an alcoholic solution of a copolymer of an N-vinyl pyrrolidone and a vinyl ester, which is useful in aerosol sprays, atornizers or can be applied directly to hair.
  • Such solution in combination with an aerosol propellant such as, for example, Freon 11, 12, 112, 113, 114, Freon C-316 and mixtures thereof, when applied to human hair, yields a glossy film which is substantially tack-free under normal conditions of relative humidity.
  • the resulting film when exposed to a relative humidity of 50% and higher contains no more than about 13% moisture and is sufliciently water-sensitive so that it can be removed from the hair by a single washing.
  • the equilibrium percentage of moisture of the copolymer is not more than one-fourth of the relative humidity. Thus, if the copolymer or film thereof is exposed to a relative humidity of 52%. the resulting film contains about 13.4% of one-fourth of the relative humidity. Thus, if the copolymer, it is not necessary to employ de-tackifying agents.
  • the weight-percent ratio of the monomers may be increased from 10 to 50% of a polymerizable vinyl ester 3 and from 50 to 90% by weight of a polymerizable N-vinyl pyrrolidone.
  • the ratio of polymerizable monomers used may range widely to yield water-sensitive to water-insoluble copolymers, both of which are soluble in alcohol and 'fluorinated alkane aerosol propellants.
  • copolymers for hair grooming preparations, we prefer to employ copolymers in which the monomers are in the ratio of 30:60 of the N-vinyl pyrrolidone and 40 to 70% by weight of the vinyl ester. In these proportions a copolymer is obtained which is readily soluble in the lower alcohols and dissolves in all of the currently employed Freons and mixtures thereof to yield a hair grooming preparation, the films of which do not become opaque or tacky at high humidities. The resulting films are glossy, tack-free and readily removed by a water wash or a water rinse.
  • copolymers utilized in preparing the film forming and hair grooming compositions of the present invention are readily prepared by copolymerizing the two monomers in the aforementioned weight-percent ratio by conventional means or in lower alcohol solvent so that the solution thereof can be used directly in the preparation of an aerosol.
  • the method of copolymerization may be either in bulk, in emulsion or in solution.
  • the monomers may be dissolved or dispersed in water or an organic solvent such as benzene, dioxane acetone, methyl ethyl ketone, ethylene dichloride or mixture of such organic solvents.
  • a polymerizing catalyst such as organic peroxides, peracids, hydroperoxides, i.e., benzoyl peroxide, lauryl peroxide,; tertiary butyl perbenzoate, hexoyl peroxide, methyl ethyl ketone peroxide, a-azodiisobutyronitrile and the like.
  • N-vinyl pyrrolidones which may be copolymerized in the aforestated concentrations with a vinyl ester, the following may be mentioned:
  • the product was recovered by evaporating the Z-butanone leaving a solid, white, clear polymer containing 75% N-vinyl-2-pyrrolidone and'25% vinyl acetate.
  • the polymer dissolved in Z-butanone gave a Fikentscher K value of 17.
  • EXAMPLE 2 A two-liter, three-necked, ground-joint, Pyrex flask equipped with two Allihn condensers, mechanical stirrer with half-moon blade, thermometer, and a nitrogen-inlet tube was charged with 139.0 grams (175 ml.) of denatured ethanol, 83.25 grams (0.75 mole) ml.) of distilled N-vinyl-Z-pyrrolidone, 64.57 grams (0.75 mole) (69.3 ml.) of vinyl acetate, distilled, and 0.75 gram of 2,2'-azodiisobutyronitrile dissolved in '30 ml. of denatured ethanol. The flask was flushed with nitrogen and the inlet rate adjusted to about 3060 bubbles per minute. The flask was heated on a steam bath of 70 C. The steam was turned off and the catalyst was added via the condenser.
  • EXAMPLE 3 Into an Autoclave Engineer steel autoclave were placed 73.80 grams of N-vinyl-2-pyrrolidone, 20.80 grams of vinyl chloride, 87.5 grams of 2-butanone and 0.410 gram of 2,2'-azodiisobutyronitrile catalyst. The autoclave was sealed and heated to 60 C. and stirred with an enamel coated stirrer for 20 hours. The autoclave was cooled to room temperature and vented into a Dry Ice trap. The trap did not gain in weight. The contents of the autoclave were poured into a tared Pyrex dish and placed in an air stream to evaporate the solvent. After 18 hours a thick syrup remained. The thick syrup was placed in a desiccator under vacuum and the remaining solvent removed.
  • the polymer obtained was a straw colored, friable material which was easily pulverized with mortar and pestle. Analysis for Volatiles indicated that the actual yield of dry polymer was 93% of the theoretical yield. Analysis for the N content bound in the polymer indicated N-vinyl-2-pyrrolidone content and 10% vinyl chloride content by difference. The polymer gave a Fikentscher K-value of 22 in water.
  • EXAMPLE 4 Into'a metal aerosol can partially submerged in a solid carbon dioxide acetone bath were condensed 40 grams of Freon 12, 40 grams of Freon 11, and to this was added 20 grams of an alcoholic solution containing a copolymer of N-vinyl-Z-pyrrolidone and vinyl acetate (Example 2). A nozzle and valve assembly was attached to the can and the entire assembly was held together in a brass cage. The can was checked for leaks by submerging in water. The aerosol sprayer was allowed to warm to room temperatu're. Glass panels were sprayed giving films which dried almost immediately to an odor-free, clear, somewhat flexible film. The films were not tacky.
  • the films when rubbed with a wet finger were not as sensitive as films containing polyvinylpyrrolidone.
  • the compounded aerosol was used to spray hair and allowed to dry.
  • the film resulting on the hair brightened and gave the hair a pleasing appearance and retained the shape and condition that the hair was held in while being sprayed. That is to say, it is useful in retaining artificial curls in hair.
  • EXAMPLE 6 Into a three-necked flask equipped with an Allihn condenser, a thermometer, a nitrogen inlet, and a mechanical stirrer was charged 55.0 grams of N-vinyl-2-pyrrolidone, 45.0 grams of vinyl propionate and 200 grams of Z-butanone. The flask was flushed with nitrogen and the inlet rate of the gas was adjusted to about 30 bubbles per minute. The flask was stirred and heated to 60 C. for 30 minutes. At this point 0.1 gram of 2,2'- azodiisobutyronitrile was added as the catalyst. The flask was stirred and maintained at 30 C. for a total of 12 hours. The polymer was recovered from the reaction solution by drying in a vacuum desiccator for 24 hours at less than 0.2 mm. of mercury vacuum.
  • the white, brittle, translucent polymer was analyzed and the analysis indicated that it contained 55% vinylpyrrolidone and 45% vinyl propionate.
  • a sample of the dried polymer gave a Fikentscher K-value of 30 in 2- butanone.
  • EXAMPLE 7 Into a 4 ounce aerosol can were condensed 25 grams of trichloromonofluoromethane and 25 grams of dichlorodifluoromethane. To this was added 6 grams of the reaction solution from Example 5, and a nozzle assembly was attached to the can and the can allowed to warm to room temperature.
  • the filled aerosol was used to spray glass panels 8 inches by 10 inches, 21 hank of human hair and a head of human hair.
  • the panels contained continuous film of the polymer and it was noticed they dried rapidly to a tack-free, transparent, odorless film.
  • the hair sprayed with the aerosol contained a clear, transparent coating which brightened the appearance of the hair. It was observed that when the head of human hair was sprayed and allowed to dry that the polymer did show hair fixative properties, that is to say, the hair coated with the polymer tended to hold the shape imposed upon it.
  • EXAMPLE 8 Into a glass aerosol compatability tube (obtained from Fischer Porter of Hatboro, Pennsylvania) was condensed, when the tube was cooled in an acetone solid carbon dioxide bath, 20 grams of trichloromonofluoromethane and 20 grams of dichlorodifluoromethane. To the tube was added 5 grams of a 50% solution of the polymer from Example 6 dissolved in anhydrous ethanol. The compatibility tube was sealed and a nozzle assembly attached to it. The completed aerosol in the compatibility tube was allowed to warm to room temperature and it was observed that a solution of all the ingredients took place.
  • the completed aerosol was used to spray a glass panel 8 inches by 10 inches and a head of human hair. A quick drying, continuous, clear, tough film was observed. It was observed that the hair was held in place by the dried coating of polymer. The polymer was observed to have hair fixing properties.
  • EXAMPLE 9 Into a metal aerosol can partially submerged into an acetone solid carbon dioxide cooling bath was condensed 35 grams of trichloromonofluoromethane, and 35 grams of dichlorodifluoromethane. To the can was added 10 grams of a 50% solution obtained from Example 2. A nozzle assembly was attached to the can and the can was sealed in a brass cage. The completed aerosol can was allowed to warm to room temperature.
  • the aerosol was used to spray a human finger and allowed to dry. It was observed for an area of about 2 square inches a clear, continuous film covered the finger. This cover could be used in place of the ordinary cloth tape bandage.
  • the aerosol was used to spray a human finger which had a slight topical cut (about A: inch long and inch deep) and it was observed that a film was obtained on the finger. The finger was sprayed after the wound had closed by coagulation of the blood. A slight smarting sensation was noticed.
  • the coating did offer protection to the wound and did not rub off if care was taken not to vigorously scrub the finger with water.
  • EXAMPLE 10 As noted in Example 4 of application, Serial No. 535,262, filed on September 19, 1955, there was prepared a complex of a copolymer of N-vinyl-2-pyrrolidone and vinyl acetate and pulverized granular iodine. Also, as noted, the iodine complex was treated at 55 C. for 4 hours and after heat treatment the complex analyzed 1.4% available iodine.
  • the aerosol was used to spray a human finger and the coating obtained was allowed to dry. A slightly brown, continuous, protective coating was obtained on about 1 square inch of the finger surface. The coating adhered well to the finger and was not sticky and did not rub oif when massaged with a dry hand. It was observed the finger could be flexed without cracking or breaking the continuous film.
  • the aerosol was used to spray a finger which had a slight surface cut (about inch long and about ,4 inch deep). The finger was sprayed after the blood had coagulated. After the film dried, it was observed that the wounded area was covered by a light brown film.
  • the solution was used to prepare an antiseptic area on human skin by applying a coating with a brush or similar instrument and allowing it to dry.
  • EXAMPLE 12 The solution given in Example 11 was used to prepare a pair of antiseptic gloves or coatings on human hands. The hands were carefully Washed and dried. The hands were then submerged into the solution and withdrawn and allowed to dry. A continuous light brown coating was obtained on the portion of the hands which had been submerged into the solution. The antiseptic coating functioned and took the place of the common surgeons rubber gloves. Any small area of the continuous film coating the hands could be easily repaired if damaged by brushing on enough of the solution to cover the damaged area and allowing it to dry to a film. The hands could be flexed and used and no cracking or peeling of the film was observed. 1 V
  • the Weight-percent ratio of the monomers is very critical and that copolymers outside the aforementioned desired ratio will lead to films which are insoluble, thereby requiring several vigorous washings before removal.
  • the desired ratio in which all of the aforementioned desired properties are found is in 30 to 60% by weight N-vinyl-Z-pyrrolidone and from 40 to 70% by weight of vinyl ester.
  • a sprayable film forming preparation substantially tack-free under normal conditions of relative humidity consisting essentially of a copolymer of 30-60% by weight of N-vinylpyrrolidone and 40-70% by weight of a vinyl ester in solution of a mixture of a low boiling aliphatic alcohol of 1 to 3 carbon atoms and at least one aerosol propellant from the class of liquified chlorofiuoro hydrocarbons of one to. two carbon atoms, the said mixture being present in sufficient amount to dissolve the said copolymer and render it sprayable, the said'vinyl ester being characterized by the following formula:
  • a sprayable hair grooming preparation substantially tack-free under normal conditions of relative humidity and having water-solubility 'for removal from the hair consisting essentially of a copolymer of N-vinylpyrrolidone and a vinyl ester in solution of a low boiling aliphatic alcohol of 1 to 3 carbon atoms and at least one aerosol propellant from the class of liquified chloro-fiuoro bydrocrabons of one to two carbon atoms, the said alcohol and propellant being present in sufficient quantities to dissolve the said copolymer and render it sprayable, said copolymer having a Fikentscher K value of 15 to 60 and consisting of from about 30 to about 60% by weight of N-vinylpyrrolidone and from about 40 to 70% I by weight of a vinyl ester'having the
  • CH CHR wherein R represents a member selected from the class consisting of chlorine, formyl, acetyl, hydroxy acetyl, propionyl and butyryl.
  • the process of keeping human hair in place which comprises spraying said hair with a fine mist dispensed fro-m an aerosol container whose essential contents consist of a volatile, chloro-fluoro-substituted lower aliphatic hydrocarbon propellent having dissolved therein a copolymer consisting of about 50% vinyl pyrrolidone and about 50% of vinyl acetate, and a low boiling aliphatic alcohol of 1 to 3 carbon atoms.
  • the process of keeping human hair in place which comprises spraying said hair with a fine mist dispensed from an aerosol container whose essential contents consist of a volatile, chloro-fluoro-substituted lower aliphatic hydrocarbon propellent having dissolved therein a copolymer consisting of about 30-90% vinyl pyrrolidone and about lO-70% by weight of vinyl acetate, and ethyl alcohol.
  • a sprayable film-forming preparation substantially tack-free under normal conditions of relative humidity consisting essentially of a copolymer of about 30 to about percent by weight of N-vinyl pyrrolidone and from about 25 to about 70 percent by weight of a vinyl ester in solution of a mixture of a low-boiling aliphatic alcohol of l-3 carbon atoms and at least one aerosol propellant from the group of liquified chloro-fluoro hydrocarbons of from 1 to 2 carbon atoms, the said mixture being present in sufiicient amount to dissolve the said copolymer and render it sprayable, the said vinyl ester being of the formula:
  • CH2 CHR V wherein R is a member of the group consisting of chloro, formyl, acetyl, hydroxy acetyl, propionyl and butyryl.
  • a sprayable film-forming preparation substantially tack-free under normal conditions of relative humidity consisting essentially of a copolymer of from about 30 to about percent by weight of N-vinyl pyrrolidone and from about 10 to about 70 percent by weight of a vinyl ester in solution ofa mixture of a low-boiling aliphatic alcohol of l3 carbon atoms and at least one aerosol propellant from the group of liquified chloro-fluoro hydrocarbons of l to 2 carbon atoms, the said mixture being present in sufficient amount to dissolve the said copolymer and render it sprayable, the said vinyl ester being of the formula:
  • R is a member of the group consisting of chloro, formyl, acetyl, hydroxy acetyl, propionyl and butyryl.
  • a sprayable film-forming preparation substantially tack-free under normal conditions of relative humidity consisting essentially of a copolymer of from about to about 60 percent by weight of N-vinyl pyrrolidone and from about to about 70 percent by weight of a vinyl ester in solution of a mixture of a low-boiling aliphatic alcohol of 1-3 carbon atoms and at least one aerosol propellant from the group of liquified chloro-fluoro hydrocarbons of 1 to 2 carbon atoms, the said mixture being present in suflicient amount to dissolve the said copolymer and render it sprayable, the said vinyl ester being of the formula:
  • CH CHR wherein R is a member of the group consisting of chloro, formyl, acetyl, hydroxy acetyl, propionyl and butyryl.
  • a sprayable hair-grooming preparation substantially tack-free under normal conditions of relative humidity and having water solubility for the removal from the hair consisting essentially of a copolymer of N-vinyl pyrrolidone and a vinyl ester in solution of a low-boiling aliphatic alcohol of 1-3 carbon atoms and at least one aerosol propellant from the group of liquified chlorofluoro hydrocarbons of 1 to 2 carbon atoms, the said alcohol and propellant being present in sufiicient quantities to dissolve the said copolymer and render it sprayable, said copolymer having a Fikentscher K value of 15 to and consisting of from about 30 to about 75 percent by weight of N-vinyl pyrrolidone and from about 25 to about percent by weight of a vinyl ester having the formula:
  • R is a member of the group consisting of chloro, formyl, acetyl, hydroxy acetyl, propionyl and butyryl.
  • a sprayable hair-grooming preparation substantially tack-free under normal conditions of relative humidity and having water solubility for removal from the hair, consisting essentially of a copolymer of N-vinyl pyrrolidone and vinyl acetate in solution of a low-boiling aliphatic alcohol of 1-3 carbon atoms and at least one aerosol propellant from the group of liquified chlorofluoro hydrocarbons of 1 to 2 carbon atoms, said copolymer having a Fikentscher K value of 15 to 60 and consisting of from about 30 to about percent by weight of N-vinyl pyrrolidone and from about 25 to about 70 percent by weight of vinyl acetate, the said mixture being present in sufficient amount to dissolve the said copolymer and render it sprayable.
  • CH CHR wherein R is a member of the group consisting of chloro, formyl, acetyl, hydroxy acetyl, propionyl and butyryl.

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  • Engineering & Computer Science (AREA)
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  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Cosmetics (AREA)
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  • Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
US621206A 1956-11-09 1956-11-09 Copolymer of vinyl pyrrolidone and vinyl acetate as aerosol hair spray Expired - Lifetime US3171784A (en)

Priority Applications (8)

Application Number Priority Date Filing Date Title
US621206A US3171784A (en) 1956-11-09 1956-11-09 Copolymer of vinyl pyrrolidone and vinyl acetate as aerosol hair spray
GB31305/57A GB828970A (en) 1956-11-09 1957-10-07 Film forming solutions of copolymers of n-vinyl pyrrolidone and n-vinyl ester
FR1187884D FR1187884A (fr) 1956-11-09 1957-10-24 Compositions d'aérosols formant des pellicules
DEG23320A DE1089930B (de) 1956-11-09 1957-11-08 Verspruehbares Haarfestlegemittel
FR828237A FR1265403A (fr) 1956-11-09 1960-05-25 Procédé de préparation de miettes de caoutchouc synthétique pour séchage
DES68680A DE1129682B (de) 1956-11-09 1960-05-25 Verfahren zum Herstellen von trockenen oder praktisch trockenen Kautschukkruemeln
BE591236D BE591236A (enrdf_load_stackoverflow) 1956-11-09 1960-05-25
GB18465/60A GB878970A (en) 1956-11-09 1960-05-25 Drying of rubber crumb

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Application Number Priority Date Filing Date Title
US621206A US3171784A (en) 1956-11-09 1956-11-09 Copolymer of vinyl pyrrolidone and vinyl acetate as aerosol hair spray
US816054A US3014898A (en) 1959-05-27 1959-05-27 Method of preparing synthetic rubber crumb for drying

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US3171784A true US3171784A (en) 1965-03-02

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US (1) US3171784A (enrdf_load_stackoverflow)
BE (1) BE591236A (enrdf_load_stackoverflow)
DE (2) DE1089930B (enrdf_load_stackoverflow)
FR (2) FR1187884A (enrdf_load_stackoverflow)
GB (2) GB828970A (enrdf_load_stackoverflow)

Cited By (9)

* Cited by examiner, † Cited by third party
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DE2022264A1 (de) * 1969-05-09 1970-11-19 Oreal Neue kosmetische Mittel und neue Copolymerisate
US4012501A (en) * 1975-05-08 1977-03-15 La Maur Inc. Hair-care composition containing a thermoplastic polymer
US4044121A (en) * 1976-03-11 1977-08-23 Minnesota Mining And Manufacturing Company Hair spray containing fluorocarbon compounds as additives
US4053696A (en) * 1974-11-30 1977-10-11 Basf Aktiengesellschaft Manufacture of vinylpyrrolidone polymers
US4272511A (en) * 1978-06-23 1981-06-09 L'oreal Cosmetic compositions for treating hair
US5304317A (en) * 1991-03-28 1994-04-19 Fospur Limited Froth flotation of fine particles
US6552142B1 (en) 1999-02-25 2003-04-22 Basf Akeiengesellschaft Process for preparing aqueous dispersions of copolymers from hydrophilic and hydrophilic monomers, copolymers obtainable therefrom and uses thereof
US20140142175A1 (en) * 2012-11-20 2014-05-22 L'oreal S.A. Anhydrous cosmetic compositions containing ascorbic acid
CN105985489A (zh) * 2015-02-15 2016-10-05 中国石油天然气股份有限公司 一种不含亚硝胺的乳液聚合集成橡胶制备方法

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1165207B (de) * 1960-03-28 1964-03-12 Gillette Co Haarfestlegemittel
DE1161660B (de) * 1960-05-03 1964-01-23 Gillette Co Haarfestlegemittel
DE1170617B (de) 1961-02-02 1964-05-21 Artos Maschb Dr Ing Meier Wind Einrichtung zum Trocknen von Kautschukkruemeln unterschiedlicher Koernung
DE1229292B (de) * 1961-06-02 1966-11-24 Basf Ag Herstellung von wasserloeslichen Verpackungs-folien
DE1243861B (de) * 1962-05-10 1967-07-06 Link Belt Co Verfahren und Vorrichtung zum Trocknen von Kautschukkruemeln
BE639300A (enrdf_load_stackoverflow) * 1962-10-29
DE1190670B (de) * 1963-01-22 1965-04-08 Huels Chemische Werke Ag Verfahren zum Trocknen von vorentwaessertem Polybutadien
US4241048A (en) * 1979-05-01 1980-12-23 Bristol-Myers Company Suspension composition of benzocaine
FR2556960B1 (fr) * 1983-12-21 1990-01-19 Tondeo France Pappert Diff Composition a base de resines carboxiliques acryliques, pour l'embellissement et le maintien de la chevelure

Citations (2)

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US2497705A (en) * 1946-10-16 1950-02-14 Du Pont Copolymerization product of n-vinyl lactams and polymerizable esters, and process for making same
US2667473A (en) * 1952-02-08 1954-01-26 Monsanto Chemicals Vinyl acetate-n-vinyl-pyrrolidone copolymers

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CH314644A (de) * 1952-11-18 1956-06-30 Lily Oil Company Mittel zur Herstellung von Überzügen
GB747806A (en) * 1953-03-27 1956-04-11 Gen Aniline & Film Corp Hair waving and setting composition
FR1101969A (fr) * 1953-06-10 1955-10-12 Bofors Ab Procédé d'obtention d'une solution plastique pouvant être utilisée comme pansement

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Cited By (9)

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Publication number Priority date Publication date Assignee Title
DE2022264A1 (de) * 1969-05-09 1970-11-19 Oreal Neue kosmetische Mittel und neue Copolymerisate
US4053696A (en) * 1974-11-30 1977-10-11 Basf Aktiengesellschaft Manufacture of vinylpyrrolidone polymers
US4012501A (en) * 1975-05-08 1977-03-15 La Maur Inc. Hair-care composition containing a thermoplastic polymer
US4044121A (en) * 1976-03-11 1977-08-23 Minnesota Mining And Manufacturing Company Hair spray containing fluorocarbon compounds as additives
US4272511A (en) * 1978-06-23 1981-06-09 L'oreal Cosmetic compositions for treating hair
US5304317A (en) * 1991-03-28 1994-04-19 Fospur Limited Froth flotation of fine particles
US6552142B1 (en) 1999-02-25 2003-04-22 Basf Akeiengesellschaft Process for preparing aqueous dispersions of copolymers from hydrophilic and hydrophilic monomers, copolymers obtainable therefrom and uses thereof
US20140142175A1 (en) * 2012-11-20 2014-05-22 L'oreal S.A. Anhydrous cosmetic compositions containing ascorbic acid
CN105985489A (zh) * 2015-02-15 2016-10-05 中国石油天然气股份有限公司 一种不含亚硝胺的乳液聚合集成橡胶制备方法

Also Published As

Publication number Publication date
GB828970A (en) 1960-02-24
FR1265403A (fr) 1961-06-30
DE1089930B (de) 1960-09-29
FR1187884A (fr) 1959-09-17
GB878970A (en) 1961-10-04
BE591236A (enrdf_load_stackoverflow) 1960-11-25
DE1129682B (de) 1962-05-17

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