CN1371268A - Cosmetic and/or pharmaceutical preparations with polymers containing polysiloxanes and the uses thereof - Google Patents

Cosmetic and/or pharmaceutical preparations with polymers containing polysiloxanes and the uses thereof Download PDF

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CN1371268A
CN1371268A CN 00812099 CN00812099A CN1371268A CN 1371268 A CN1371268 A CN 1371268A CN 00812099 CN00812099 CN 00812099 CN 00812099 A CN00812099 A CN 00812099A CN 1371268 A CN1371268 A CN 1371268A
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acid
preparation
luviflex
silk
purposes
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CN1194024C (en
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W·M·道施
J·恩格瑟
H·维特勒
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BASF SE
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BASF SE
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    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/89Polysiloxanes
    • A61K8/891Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone
    • A61K8/894Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone modified by a polyoxyalkylene group, e.g. cetyl dimethicone copolyol
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/24Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing ingredients to enhance the sticking of the active ingredients
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K47/00Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
    • A61K47/30Macromolecular organic or inorganic compounds, e.g. inorganic polyphosphates
    • A61K47/32Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. carbomers, poly(meth)acrylates, or polyvinyl pyrrolidone
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K47/00Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
    • A61K47/30Macromolecular organic or inorganic compounds, e.g. inorganic polyphosphates
    • A61K47/34Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polyesters, polyamino acids, polysiloxanes, polyphosphazines, copolymers of polyalkylene glycol or poloxamers
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/81Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • A61K8/8141Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • A61K8/8147Homopolymers or copolymers of acids; Metal or ammonium salts thereof, e.g. crotonic acid, (meth)acrylic acid; Compositions of derivatives of such polymers
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/81Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • A61K8/8141Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • A61K8/8152Homopolymers or copolymers of esters, e.g. (meth)acrylic acid esters; Compositions of derivatives of such polymers
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/81Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • A61K8/8141Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • A61K8/8158Homopolymers or copolymers of amides or imides, e.g. (meth) acrylamide; Compositions of derivatives of such polymers
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/81Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • A61K8/817Compositions 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)
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/81Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • A61K8/817Compositions 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)
    • A61K8/8182Copolymers of vinyl-pyrrolidones. Compositions of derivatives of such polymers
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/87Polyurethanes
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K9/00Medicinal preparations characterised by special physical form
    • A61K9/0012Galenical forms characterised by the site of application
    • A61K9/0014Skin, i.e. galenical aspects of topical compositions
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q1/00Make-up preparations; Body powders; Preparations for removing make-up
    • A61Q1/02Preparations containing skin colorants, e.g. pigments
    • A61Q1/10Preparations containing skin colorants, e.g. pigments for eyes, e.g. eyeliner, mascara
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00Preparations for care of the hair
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00Preparations for care of the hair
    • A61Q5/02Preparations for cleaning the hair
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00Preparations for care of the hair
    • A61Q5/06Preparations for styling the hair, e.g. by temporary shaping or colouring
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/12Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes

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  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • Veterinary Medicine (AREA)
  • Public Health (AREA)
  • Epidemiology (AREA)
  • Birds (AREA)
  • Chemical & Material Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Pharmacology & Pharmacy (AREA)
  • Inorganic Chemistry (AREA)
  • Toxicology (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Dermatology (AREA)
  • Polymers & Plastics (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Organic Chemistry (AREA)
  • Proteomics, Peptides & Aminoacids (AREA)
  • Dentistry (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Cosmetics (AREA)
  • Medicinal Preparation (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polymerisation Methods In General (AREA)
  • Graft Or Block Polymers (AREA)
  • Silicon Polymers (AREA)

Abstract

The invention relates to cosmetic and/or pharmaceutical preparations composed of polymers containing polysiloxanes which are soluble in water or can be dispersed therein, in addition to other polymers and /or filters protecting against ultraviolet light. The invention also relates to the use of such preparations and the use of polymers containing polysiloxanes.

Description

Comprise the cosmetics of the polymer that contains polysiloxanes and/or pharmaceutical preparation and uses thereof
The present invention relates to comprise the cosmetics and/or the pharmaceutical preparation of the polymer that contains water solublity or water dispersible polysiloxanes and other polymer and/or anti-UV light filtrate (filter).The invention still further relates to the purposes of these preparations and contain the purposes of the addition polymers of polysiloxanes.
Polymer with filming performance is used in cosmetics and/or the pharmaceutical preparation, and is particularly suitable as the additive of hair and cosmetics for skin.
Be used for the cosmetic formulations of skin, polymer can show sp act.These polymer especially help to moisturize the skin and regulate, and improve dermal sensation.It is more smooth and more soft that skin becomes.
Be used for the cosmetic formulations of hair, with polymer be used to finalize the design, the structure of molding and improvement hair.But they improve cardability and improve the sensation of hair.These hair-treatment compositions generally include the solution of film former in the mixture of alcohol or alcohol and water.
A requirement to hair-treatment composition is that they especially give hair gloss, pliability and active naturally sensation.
Homopolymerization of known use vinyl lactam and copolymer or contain the polymer of carboxylate.Required performance characteristic, as the strong constancy under high atmospheric humidity, elasticity, can from hair wash off and with the compatibility of other furnish component,, elastification hydrophobic by copolymerization and carboxylic monomeric mixture are realized.
Yet, use the hair style typing of these polymer to feel coarse unhappyly and unnatural.Although add the sensation that softening agent can improve this hair style, reduced styling simultaneously.
Usually use polysiloxanes, although these polysiloxanes and polar polymer are incompatible, therefore for making it can prepare other additives of common needs fully.Store and separation problem can occur between the operating period in batching.
For preventing to separate, therefore attempt polysiloxane group and polymer covalent bond always.EP-A 408 311 has described the graft copolymer with carbon backbone chain of bonding polydimethylsiloxane side chain on it.Polymer with the unsaturated monomer preparation that has polysiloxane chain has only been described.Graft copolymer with carbon backbone chain of bonding polydimethylsiloxane side chain on it is not described.
EP-A 670 342 has described alkoxylated polysiloxane has been used for hair care composition.Be not disclosed in the addition polymers that uses unsaturated compound in the hair care composition.Really improve its sensation although alkoxylated polysiloxane is used as the additive of commercial hair fixing copolymer, caused styling to reduce simultaneously.
European patent EP-A 412 704 and EP-A 412 707 have described the polysiloxane group that molal weight is 1000 to 50,000 macromonomer form, with itself and habitual hydrophobic and polymerizable hydrophilic monomer.Synthetic these monomers are complicated especially.Because of its high molecular, therefore can not from polymer, isolate unreacted monomer and unreactive impurities thereof basically.These have represented toxicity and allergenicity danger.In addition, for obtaining good effect, the copolymer of acquisition usually must be only and other polymer, carrier and other auxiliary agent formulated in combination, as above-mentioned patent instruction.
DE 42 40 108 discloses and has been suitable as antifouling paint, particularly as the anti-polyorganosiloxane adhesive that contains of scribbling coating.Yet these binding agents are similar to varnish and are not suitable for the cosmetics purpose.
WO 99/04750 has described can be by containing the polymer that the radical polymerization ethylenically unsaturated monomer obtains in the presence of the polyorganosiloxane ramification of polyalkylene oxide.
The invention provides the purposes of addition polymers in pharmaceutical preparation that can obtain by the monomer mixture of radical polymerization (a) ethylenically unsaturated monomer and the polyorganosiloxane ramification that (b) contains polyalkylene oxide.
Because of a variety of causes, solid pharmaceutical preparation such as tablet, capsule, pill, granule, crystal etc. are coated with the film coating, the film coating promptly is set.Can cover odour nuisance or taste in this way, and improve swallowing property.The stability of active component can improve by coating, and reason is seldom to have water vapour and oxygen to import in the tablet.These preparations have preferably outward appearance and can distinguish better by adding dyestuff.In addition, the rate of release of active component can be regulated by the film coating especially.
Difference is promptly to release between (Instant-Release) dosage form and the slow release formulation usually.
For immediate release dosage form, disintegration of tablet and active component discharge from preparation if possible and should not influenced by coating, so reason film coating must be dissolved in the gastric juice fast.In addition, must have good film properties.Hot strength and elongation at break should be high, and the film coating can bear in the packing of for example medicine processing-especially-and the mechanism of transportation or lay up period generation like this.
The product that is usually used in the immediate-release tablet formulations coating is hydroxypropyl emthylcellulose (HPMC).Hydroxypropyl emthylcellulose presents viscosity along with concentration in aqueous solution raises and sharply raises.Hydroxypropyl cellulose (HPC) also presents similar behavior.
Because must be with the fine atomizing during tablet coats of film former solution, and the drop that forms must make the thorough moistening of tablet surface, must fully launch simultaneously, viscosity must be no more than certain limit (between 150 to 250mPas), depends on bleed type and device.Therefore, only can use lower film former concentration for HPMC.
The Pharmacoat that recommends in the document The concentration of 606 (Shin-etsu) is 5 to 7wt% (" pharmaceutical pack coating techniques ", Graham Cole writes, the technical data handbook of Taylor and Francis Ltd.1995 and manufacturer).These low spraying concentration cause long process time and therefore cause expensive.
In addition, hydroxypropyl emthylcellulose is especially at wettability, exist other shortcoming aspect the caking property on the tablet surface, pigment binding ability, thin film mechanical performance, hygroscopicity, permeability, rate of dissolution and film-coated tablets to water vapour and oxygen and the disintegration time difference between the core.
Low elasticity by the thin film of hydroxypropyl emthylcellulose preparation usually causes film-coated tablets to split under wet condition at lay up period, and the result makes the core swelling.For this problem, even use plasticizer also only can cause inappreciable improvement.On the contrary, it can cause films tacky, and because migration causes tablet properties to change.
The oral pharmaceutical form (being generally the slow releasing pharmaceutical form) that medicine is discharged for the effect that prolongs active component in long-time becomes more and more important.Their favourable part is owing to take the low compliance of patients of therefore having improved of frequency; Owing to having avoided plasma peaks to reduce side effect; The haemoconcentration of medicine is more even and avoided local excitation.Except preparation use insoluble but semi-permeable or contain the containing the drug core of film coating in hole through the water of its diffusion medicine, by medicine being imbedded in the matrix may command and being postponed to discharge.In addition, can make spent ion exchange resin and treatment system (for example OROS).
Medicine is provided by the advantage that provides especially in the hydrocolloid matrix is: the drug safety (reason is can not produce the dosage effect of coming down in torrents) of simple and low-cost manufacture method and high level.Be generally used for the auxiliary agent of this purpose such as hydroxypropyl emthylcellulose (HPMC), hydroxypropyl cellulose, alginic acid or alginate and xanthan gum and have shortcoming in use.Those shortcomings that can mention are the not enough mobile performances that hinder direct compression, and drug release is to the dependency of the pH of osmolarity (salt content) and release medium.This is equally applicable to HPMC, hydroxypropyl cellulose, xanthan gum and alginate.Use xanthan gum also can cause the soft tablet, and alginate direct compression cause only the having slight sustained release performance briquetting of (the longest 8 hours).Natural swelling material (for example alginate) shows the wide variability between each batch of material.
Binding agent is used for pharmaceutical preparation improves machinability and mechanical strength.Usually they are used for tablet, granule and pill, and obtain improved flowability, higher fracture strength and lower fragility.
Binding agent that uses such as maltodextrin or polyvinylpyrrolidone usually cause not satisfied fracture strength and fragility at present.Other binding agent such as gelatinized corn starch and hydroxypropyl emthylcellulose (HPMC) only can use by low concentration because of its high viscosity.
In addition, coalescents is used with solution and spray liquid form, be applied to it on skin or the mucosa or whole body is introduced in the body.Its example is the preparation that is used for Wound healing and bone regeneration and spraying dressing, and is applied to the preparation on intact skin or the mucosa.Here, skin is protected by thin film, and active component is permeable goes into skin.
For transdermal therapeutic system with for the wound Gypsum Fibrosum, similar with above-mentioned preparation, need high-flexibility, but the product that obtains at present there is not this performance.Use possible plasticizer for obtaining required pliability, consider it is unfavorable from toxicity and pharmacology.
An object of the present invention is to provide as coating materials, binding agent and/or film former in the pharmaceutical preparation and water solublity or the aqueous dispersion polymers that does not have above-mentioned shortcoming.
We find that surprisingly addition polymers of the present invention is applicable to pharmaceutical preparation.
They are especially suitable for use as coating materials, binding agent and/or film former in the pharmaceutical preparation.They are particluarly suitable for being used as in the oral drug preparation matrix that discharges active component.
Polymer of the present invention can be used in the high amount of drug preparation.
For example, as coated preparation, can mention film-coated tablets, peplos micro-tablet, sugar coated tablet, coating lozenge, capsule, crystal, granule or pill.
The preparation that contains binding agent is for example tablet, micro-tablet, core, granule or pill.
In addition, polymer of the present invention can be used for preparation and is applied on skin or the mucosa and film forming solution and spray liquid.Because huge extendability and caking property, this thin film and skin or mucosa adhere to for a long time.Therefore reduction can be applied frequency, and improve and dress comfortableness.Its example is spraying dressing, the spray of sterilizing, the solution that contains mycostat that are used for wound, contain antibiotic mouthful of spray or solution etc.Because of its pliability, the application in transdermal therapeutic system also is favourable.
Being used for polymer of the present invention makes the oil-wetted surface moistening easily and has good protecting colloid performance.In the time of in adding suspension and emulsion, they itself with the particle adhesion of decentralized photo and make it stable.Therefore they can be used as wetting aid and stabilizing agent in dispersion.
By with the drug interaction that is slightly soluble in water, therefore they have improved the dissolubility and the rate of dissolution of described material, have improved the absorbability and the bioavailability of medicine.This advantageous effects therein active component not for being tangible in the preparation of dissolved form such as tablet, granule, suspension etc.
Can process with active component being used for polymer of the present invention (if suitable other auxiliary agent that also is mixed with); obtain polymer/active component melt; it is extruded or roll obtain medicine; or pulverizing obtains granule or powder after extruding; only processing obtains medicament forms then, and for example compacting obtains tablet.Here, polymer of the present invention is brought top listed performance in the preparation into.
In various pharmaceutical preparatioies, polymer of the present invention satisfies following function with good way:
The biological adhesive that the solubilizer of dispersing aid, suspension aids, wetting agent, slightly soluble medicine, emulsifying agent, crystallization inhibitor, agglomeration resistance auxiliary agent, protecting colloid, prolongation and enhancing contact with mucosa, coating additive, viscosity modifier, be used for preparing the solid solution that contains medicine auxiliary agent, be used to regulate the auxiliary agent that the active component of slow release batching discharges.
Insoluble or only slightly soluble but dispersible polymer of the present invention also can be used as release polymer and as the binding agent of active component plaster in water.
When being used to prepare suppository and vaginal suppository, these polymer are guaranteed the pliability of preparation on the one hand, promote active ingredient disintegrate and dissolving on the other hand, and they are with strengthening the film coating mucosa that contains active component that absorbs.
Tablet is swelling in various degree, depends on auxiliary agent and active ingredient, period of storage and storage requirement such as the temperature and humidity of use.Be full of cracks appears in the dura mater coating during the core swelling.Therefore, the elasticity of film former is an important parameter.
Polymer can be applied on the core that contains active ingredient with pure form or with conventional auxiliary agent.The example of conventional auxiliary agent is to be used for painted color pigment, be used to increase the Chinese white such as the titanium dioxide of coverage rate, as the Talcum and the silicon dioxide that do not glue reagent, as Polyethylene Glycol, glycerol, propylene glycol, glycerol triacetate, the triethyl citrate of plasticizer be used to improve various surfactants such as sodium lauryl sulfate, polysorbate 80, Pluronics and the Cremophores of wettability.These materials that provide are not as an example represented restriction.
Can use all additives known of the film coating that is fit to dissolve in gastric juice.
Spendable coating method is a customary way, and as coating in fluid bed or horizontal rotary drum coating machine, dip-coating method and dish are coated with method.Except using on tablet, polymer of the present invention also can be used for coating other medicines preparation, as granule, pill, crystal or capsule.In the usual way with 5 to 200 μ m, the thickness of preferred 10 to 100 μ m applies with coating materials of the present invention.
When the binding agent,, distinct between the wet and dried binding agent according to processing method.The latter is particularly useful for direct compression and does pelletize and compression.Here binding agent is mixed direct compression, or pelletize then and compression with active ingredient and non-essential other auxiliary agents.
On the contrary, in wet pelletize, active ingredient/agent mixture with the solution-wet of binding agent in water or organic solvent, and is sieved the material of moistening, dry then.Moistening and drying also can be parallel carrying out in the fluidized bed prilling for example.
For optimizing processing, binding agent should have low viscosity in solution, because viscous solution causes uneven grain.
Binding agent should obtain uniform hard, wear-resistant granule or tablet.For tablet, fracture strength is even more important especially, because a lot of active ingredient is difficult to compacting, therefore makes tablet mechanical stability deficiency.
In addition, the rate of release of pharmaceutical preparation disintegrate and active ingredient should obviously be subjected to the binding agent adverse effect.
Modal binding agent is a polyvinylpyrrolidone for example, vinyl acetate/vinylpyrrolidone copolymer, gelatin, gelatinized corn starch, maltodextrin, hydroxyalkylation or carboxylation alkylation cellulose derivative such as hydroxypropyl emthylcellulose, methylcellulose, sodium carboxymethyl cellulose and natural gum type such as Radix Acaciae senegalis, pectin or alginate.
Much in solution, have a high viscosity in these binding agents, therefore be difficult to processing.Because therefore high viscosity wants the bad and inhomogeneous moistening of powder particle of pelletize, cause granule strength too low unfavorable with particle size distribution.
In addition, a lot of binding agents be moisture absorption and absorb swelling behind the water.This can significantly change the performance of granule and tablet.
Find that surprisingly polymer of the present invention has the excellent results as binding agent, and be 0.5 to 20wt% during preferred 1 to 10wt% (by the batching gross weight) disintegrate to be had slight influence in concentration.In addition, because its good wettability can improve the release of slightly soluble active ingredient.
When these polymer were used as binding agent, gained granule and tablet had outstanding mechanical stability, and stable equally in long time stored.
Another object of the present invention provides some new preparation types, and these preparations especially can improve hair nursing and skin nursing.
Wherein interestedly especially also be to provide preparation with improved film property.This is for pharmaceutical preparation and cosmetic formulations, and for example particularly ultraviolet screening agent and decorative cosmetic product having all are interested.Here secondly at first attempt to obtain to need to improve the effect of medicine and/or cosmetic ingredient at the preparation that does not have the stable storage of preparation under the strict restriction.
Particularly, improve the performance of hair care composition.
We find, and these purposes are by comprising at least a can the realization by the polymer that obtains at the monomer mixture that contains radical polymerization ethylenically unsaturated monomer in the presence of the polysiloxanes of polyalkylene oxide and the preparation of another polymer.
The invention provides the preparation that comprises these polymer and another polymer, this another polymer is selected from:
Polyvinylpyrrolidone;
The polyethylene caprolactam;
Polyurethane;
The copolymer of acrylic acid, methyl methacrylate, octyl acrylamide, methacrylic acid fourth amino ethyl ester and hydroxypropyl methacrylate;
The copolymer of tert-butyl acrylate, ethyl acrylate and methacrylic acid;
The copolymer of ethyl acrylate and methacrylic acid;
N tert butyl acrylamide, ethyl acrylate and acrylic acid copolymer;
The copolymer of vinyl acetate and .beta.-methylacrylic acid and/or neodecanoic acid (vinyl) ester;
Vinyl acetate and/or propionate and N-vinylpyrrolidone copolymers.
We find surprisingly, comprise that the preparation of this polymer and these other polymer has beyond thought performance.Preparation of the present invention with regard to its skin nursing and hair nursing performance, is better than prior art formulations especially.They have very good filming performance and shaping performance in addition.
The copolymer of tert-butyl acrylate, ethyl acrylate and methacrylic acid (INCI title: acrylate copolymer) for example can trade name Luvimer TM100P, Luvimer TM36D, Luvimer TM30E (BASF) is commercial.
The copolymer of ethyl acrylate and methacrylic acid (INCI title: acrylate copolymer) for example can trade name Luviflex TMSoft (BASF) is commercial.
N tert butyl acrylamide, ethyl acrylate and acrylic acid copolymer (INCI title: acrylate/acrylamide copolymer) for example can trade name Ultrahold Strong TM, Ultrahold 8 TM(BASF) commercial.
Polyvinylpyrrolidone (INCI title: PVP) for example can trade name Luviskol K TM, Luviskol K 30 TM(BASF) and PVP K (ISP) commercial.
Polyethylene caprolactam (INCI: the polyethylene caprolactam) for example can trade name Luviskol Plus TM(BASF) commercial.
The copolymer of vinyl acetate and .beta.-methylacrylic acid (INCI:VA/ crotonates/copolymer) for example can trade name Luviset CA 66 TM(BASF), Resyn TM28-1310 (NationalStarch) and Aristoflex TMA (Celanese) is commercial.
The copolymer of vinyl acetate .beta.-methylacrylic acid and neodecanoic acid (vinyl) ester (INCI:VA/ crotonates/neodecanoic acid ester copolymer) for example can trade name Resyn TM28-2930 (National Starch) and Luviset TMCAN (BASF) is commercial.
Vinyl acetate and N-vinylpyrrolidone copolymers (INCI:PVP/VA) for example can trade name Luviskol VA TM(BASF) and PVP/VA (ISP) commercial.
Polyurethane (INCI: polyurethane-1) for example can trade name Luviset TMPUR is commercial.
The copolymer of acrylic acid, methyl methacrylate, octyl acrylamide, methacrylic acid fourth amino ethyl ester and hydroxypropyl methacrylate (INCI: octyl acrylamide/acrylate/methacrylic acid fourth amino ethyl ester copolymer) for example with trade name Amphomer TM28-4910 and Amphomer TMLV-71 (National Starch) is commercial.
Particularly preferred another polymer is those copolymers that contain vinyl acetate.
The invention further relates to the purposes of these preparations in cosmetics and/or pharmaceutical preparation.
The present invention also provides the preparation that comprises polymer of the present invention and at least a anti-UV light filtrate, relates to its purposes in cosmetics and/or pharmaceutical preparation.
The filtrate against sunshine that is used for cosmetics and pharmaceutical preparation prevents or reduces the degree of sunlight to the adverse effect of application on human skin at least.In addition, these filtrate against sunshine also play and prevent that its composition from being decomposed by the UV irradiation or the effect of degraded.In the cosmetic hair batching, purpose is to prevent that keratin fiber from being destroyed by the UV ray.
The sunlight that reaches earth surface have a certain proportion of directly near the UV-B ray (280 to 320nm) of visible region and UV-A ray (>320nm).Influence to application on human skin is confirmed by sunburn under the UV-B ray especially.
The narrower zone of the active maximum of the erythema of sunlight around 308nm provides.
For preventing the UVB ray, known a lot of chemical compounds; These chemical compounds especially are the derivant of 3-benzylidene camphor, 4-amino benzoic Acid, cinnamic acid, salicylic acid, benzophenone and 2-Phenylbenzimidazole.
For the zone (UVA district) of about 320nm between about 400nm, also importantly has obtainable filtrate, because ray that should the zone can initiation reaction under heliosensitivity skin.Find that the UVA ray causes the elasticity and the collagen fiber infringement of connective tissue, so causes the skin premature aging, and thinks and cause multiple phototoxicity and photo sensitive reaction.Harmful effect of UVB ray can strengthen by the UVA ray.
Although the preparation that much contains anti-UV light filtrate known in the state of the art, but still need relate to the improvement preparation of following performance: the stability of the stability of batching, anti-UV light filtrate, reach the anti-light factor with the maximum possible of minimum possible anti-UV light filtrate concentration coupling.Prior art formulations has anti-UV light filtrate and skin and the not satisfied adhesion of hair especially.
This means the long-time protection that to guarantee skin and hair.Therefore a purpose provides the preparation with described shortcoming.In addition, should without a doubt preparation be added in the habitual batching.
These purposes realize by the preparation that comprises following component:
-can be by the polymer of the following monomeric monomer mixture acquisition of radical polymerization
(a) ethylenically unsaturated monomer
(b) contain the polyorganosiloxane ramification of polyalkylene oxide
-anti-UV light filtrate.
Spendable anti-UV light filtrate is oil-soluble organic UV-A filtrate and/or UV-B filtrate and/or water solublity organic UV-A filtrate and/or UV-B filtrate.The total amount of anti-UV light filtrate is generally 0.1 to 30wt%, and preferred 0.5 to 15wt%, and particularly 1 to 10wt%, by the gross weight of preparation.
Anti-UV light filtrate is advantageously chosen in such a way: promptly these preparations are protected skin in the entire ultraviolet radiation scope.
Its example is:
Sequence number Material CAS No. (=acid)
1 The 4-amino benzoic Acid 150-13-0
2 3-(4 '-trimethyl ammonium) benzal camphane-2-ketone Methylsulfate 52793-97-2
3 Salicylic acid 3,3,5-trimethylcyclohexyl (Homosalatum) 118-56-9
4 2-hydroxyl-4-methoxy benzophenone (Oxybenzonum) 131-57-7
5 2-Phenylbenzimidazole-5-sulfonic acid and potassium, sodium and triethanolamine salt 27503-81-7
6 3,3 '-(1,4-phenylene two methines) two (7,7-dimethyl-2-oxo dicyclo [2.2.1] heptane-1-methanesulfonic acid) and salt thereof 90457-82-2
7 The two many ethoxy ethyl esters of (many ethyoxyls) amino benzoic Acid of 4- 113010-52-9
8 4-dimethylaminobenzoic acid 2-Octyl Nitrite 21245-02-3
9 Salicylic acid 2-Octyl Nitrite 118-60-5
10 4-methoxy cinnamic acid 4-isopentyl ester 71617-10-2
11 4-methoxy cinnamic acid 2-Octyl Nitrite 5466-77-3
12 2-hydroxyl-4-methoxy benzophenone-5-sulfonic acid (Sulisobenzonum) and sodium salt thereof 4065-45-6
13 3-(4 '-sulfo group) benzal camphane-2-ketone and salt thereof 58030-58-6
14 3-benzal camphane-2-ketone 16087-24-8
15 1-(4 '-isopropyl phenyl)-3-phenyl-propane-1, the 3-diketone 63260-25-9
16 Salicylic acid 4-isopropyl benzyl ester 94134-93-7
17 2,4,6-triphen amido (neighbour-carbonyl-2 '-ethylhexyl-1 '-the oxygen base)-1,3,5-triazines 88122-99-0
18 3-imidazol-4 yl acrylic acid and ethyl ester thereof 104-98-3
19 Ortho-aminobenzoic acid cover basic ester or: 5-methyl-2-(1-Methylethyl)-2-Aminobenzoate 134-09-8
20 Para-amino benzoic acid glyceride or: 4-amino benzoic Acid 1-glyceride 136-44-7
21 2,2 '-dihydroxy-4-methoxy benzophenone (Dioxybenzone) 131-53-3
22 2-hydroxyl-4-methoxyl group-4-methyldiphenyl ketone (Mexenon) 1641-17-4
23 The triethanolamine Salicylate 2174-16-5
24 The Dimethoxyphenyl glyoxalic acid or: 3,4-Dimethoxyphenyl glyoxalic acid sodium 4732-70-1
25 3-(4 '-sulfo group) benzal camphane-2-ketone and salt thereof 56039-58-8
26 2,2 ', 4,4 '-tetrahydroxybenzophenone 131-55-5
27 2,2 '-di-2-ethylhexylphosphine oxide [6 (2H-benzotriazole-2-yl)-4-(1,1,3, the 3-tetramethyl butyl) phenol] 103597-45-1
28 2,2 '-(1, the 4-phenylene) two-1H-benzimidazole-4,6-disulfonic acid, Na salt 180898-37-7
29 2, two [4-(2-ethyl hexyl oxy)-2-hydroxyl] phenyl-6-(4-methoxyphenyl) of 4--(1,3,5) triazine 187393-00-6
30 3-(4-methyl benzal) Camphora 36861-47-9
31 The two many ethoxy ethyl esters of (many ethyoxyls) para-amino benzoic acid of 4- 113010-52-9
32 2, the 4-dihydroxy benaophenonel 131-56-6
33 2,2 '-dihydroxy-4,4 '-dimethoxy-benzophenone-5,5 '-disodium sulfonate 3121-60-6
Other combinative preventing light agent especially is following chemical compound:
Figure A0081209900221
Above-mentioned can be of course not restrictive with the anti-UV light filtrate of addition polymers of the present invention and usefulness.
The present invention further provides the purposes of these preparations in cosmetics and/or pharmaceutical preparation.Polymer
Suitable polymerisable monomer (a) is an ethylenically unsaturated monomer.To this, can use single monomer or two or more monomeric mixture.
Can be preferred by the polymeric monomer of radical initiation reaction.The term ethylenically unsaturated monomer is meant that monomer has at least one can be single-, two-, three-or quaternary polymerizable carbon-to-carbon double bond.
Ethylenically unsaturated monomer (a) can be described by following general formula:
X-C(O)CR 7=CHR 6
Wherein:
X is selected from-OH ,-OM ,-OR 8, NH 2,-NHR 8, N (R 8) 2
M is for being selected from Na +, K +, Mg ++, Ca ++, Zn ++, NH 4 +, alkylammonium, dialkyl ammonium, trialkyl ammonium and tetra-allkylammonium cation;
Radicals R 8Can be and be selected from-H, C 1-C 40Straight or branched alkyl, N, the identical or different group of N-dimethylaminoethyl, 2-ethoxy, 2-methoxy ethyl, 2-ethoxyethyl group, hydroxypropyl, methoxy-propyl or ethoxycarbonyl propyl;
R 7And R 6Be selected from independently of each other-H, C 1-C 8Straight or branched alkyl, methoxyl group, ethyoxyl, 2-hydroxyl-oxethyl, 2-methoxy ethoxy and 2-ethoxyethyl group.
The representativeness of suitable monomers (a) but non-limitative example are for example acrylic acid and salt, ester and amide.These salt can or replace the ammonium counter ion counterionsl gegenions derived from any required no noxious metals, ammonium.
Ester can be derived from C 1-C 40Straight chain, C 3-C 40Side chain or C 3-C 40Carbocyclic alcohol, derived from having 2 to the polyfunctional alcohol of about 8 hydroxyls such as ethylene glycol, hexanediol, glycerol and 1,2, the 6-hexanetriol is derived from amino alcohol or alcohol ether such as methyl cellosolve and ethoxy ethanol or Polyethylene Glycol.
That same suitable is the acrylic acid of general formula (II) and the N of methacrylic acid, N-dialkyl amino Arrcostab and N-dialkyl aminoalkyl acrylamide and Methacrylamide
Figure A0081209900231
R wherein 9=H, have the alkyl of 1 to 8 carbon atom,
R 10=H, methyl,
R 11=have an optional alkylidene that is replaced by alkyl of 1 to 24 carbon atom,
R 12, R 13=C 1-C 40Alkyl,
Z=nitrogen, wherein x=1; Or oxygen, wherein x=0
Amide can be unsubstituted, the N-alkyl-the N-alkyl amino is mono-substituted, or N, the N-dialkyl group replaces or N, the N-dialkyl amido is dibasic, and wherein alkyl or alkylamino are derived from C 1-C 40Straight chain, C 3-C 40Side chain or C 3-C 40The carbocyclic ring unit.In addition, alkylamino can be by quaternized.
The preferred monomers of general formula I I is (methyl) acrylic acid N, N-dimethylamino methyl ester, (methyl) acrylic acid N, N-lignocaine methyl ester, (methyl) acrylic acid N, N-dimethylaminoethyl, (methyl) acrylic acid N, N-lignocaine ethyl ester.
Spendable other monomers (a) are acrylic acid and salt, ester and the amide that replaces, and wherein the substituent group on carbon atom is in acrylic acid two or three, and is selected from C independently of each other 1-C 4Alkyl ,-CN, COOH, special preferable methyl acrylic acid, ethylacrylic acid and 3-alpha-cyanoacrylate.These salt, ester and the amide of these substitutional crylic acids can be selected from salt, ester and the amide of aforesaid propylene acid.
Other suitable monomers (a) is C 1-C 40Straight chain, C 3-C 40Side chain or C 3-C 40The vinyl esters of carbocyclic ring carboxylic acid and allyl ester (for example vinyl acetate, propionate, new n-nonanoic acid vinyl acetate, new hendecanoic acid vinyl acetate or p t butylbenzoic acid vinyl acetate); Vinyl or allyl halide, preferred vinyl chloride and allyl chloride, vinyl ethers, preferable methyl, ethyl, butyl or dodecyl vinyl, vinyl formamide, vinyl methylacetamide, vinyl amine; Vinyl lactam, preferred vinyl ketopyrrolidine and caprolactam, vinyl-or the heterocyclic compound that replaces of pi-allyl, optimal ethylene yl pyridines, second alkene oxazolin and allyl pyridine.
That same suitable is the N-vinyl imidazole of general formula III, wherein R 14To R 16Be hydrogen, C independently of each other 1-C 4-alkyl or phenyl:
Figure A0081209900241
Other suitable monomers (a) are the diallylamines of general formula (IV):
Figure A0081209900242
R wherein 17=C 1-C 24-alkyl
Other suitable monomers (a) are vinylidene chlorides; With hydrocarbon with at least one carbon-to-carbon double bond, optimization styrene, α-Jia Jibenyixi, t-butyl styrene, butadiene, isoprene, cyclohexadiene, ethylene, propylene, 1-butylene, 2-butylene, isobutene., vinyltoluene and these monomeric mixture.
Specially suitable monomer (a) is an acrylic acid, methacrylic acid, ethylacrylic acid, acrylic acid methyl ester., ethyl acrylate, propyl acrylate, n-butyl acrylate, Isobutyl 2-propenoate, the acrylic acid tertiary butyl ester, 2-EHA, decyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-BMA, isobutyl methacrylate, the metering system tert-butyl acrylate, methacrylic acid 2-Octyl Nitrite, decyl-octyl methacrylate, the ethylacrylic acid methyl ester, the ethyl propylene acetoacetic ester, the positive butyl ester of ethylacrylic acid, the ethylacrylic acid isobutyl ester, the ethyl propylene tert-butyl acrylate, ethylacrylic acid 2-Octyl Nitrite, ethylacrylic acid ester in the last of the ten Heavenly stems, acrylic acid 2,3-dihydroxy propyl ester, methacrylic acid 2,3-dihydroxy propyl ester, acrylic acid 2-hydroxy methacrylate, Hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, ethylacrylic acid 2-hydroxy methacrylate, acrylic acid 2-methoxyl group ethyl ester, methacrylic acid 2-methoxyl group ethyl ester, ethylacrylic acid 2-methoxyl group ethyl ester, methacrylic acid 2-ethoxy ethyl ester, ethylacrylic acid 2-ethoxy ethyl ester, methacrylic acid hydroxyl propyl ester, single acrylic acid glyceride, monomethyl acrylic acid glyceride, (methyl) acrylic acid poly alkylene glycol ester, unsaturated sulfonic acid such as acrylamido propane sulfonic acid;
Acrylamide, Methacrylamide, ethyl acrylamide, N methacrylamide, N, the N-DMAA, the N-ethyl acrylamide, the N-N-isopropylacrylamide, N-butyl acrylamide, N tert butyl acrylamide, the N-octyl acrylamide, uncle's N-octyl acrylamide, N-octadecyl acrylamide, N phenyl acrylamide, N-methyl acrylamide, N-ethyl-methyl acrylamide, N-dodecyl methyl acrylamide, the 1-vinyl imidazole, 1-vinyl-glyoxal ethyline, (methyl) acrylic acid N, N-dimethylamino methyl ester, (methyl) acrylic acid N, N-lignocaine methyl ester, (methyl) acrylic acid N, N-dimethylaminoethyl ester, (methyl) acrylic acid N, N-diethyllaminoethyl ester, (methyl) acrylic acid N, N-dimethylamino butyl ester, (methyl) acrylic acid N, N-lignocaine butyl ester, (methyl) acrylic acid N, N-dimethylamino hexyl ester, (methyl) acrylic acid N, N-dimethylamino octyl group ester, (methyl) acrylic acid N, N-dimethylamino dodecyl ester, N-[3-(dimethylamino) propyl group] Methacrylamide, N-[3-(dimethylamino) propyl group] acrylamide, N-[3-(dimethylamino) butyl] Methacrylamide, N-[8-(dimethylamino) octyl group] Methacrylamide, N-[12-(dimethylamino) dodecyl] Methacrylamide, N-[3-(lignocaine) propyl group] Methacrylamide, N-[3-(lignocaine) propyl group] acrylamide;
Maleic acid, fumaric acid, maleic anhydride and monoesters thereof .beta.-methylacrylic acid, itaconic acid, diallyldimethylammonium chloride, vinyl ethers (for example methyl, ethyl, butyl or dodecyl vinyl), vinyl formamide, vinyl methylacetamide, vinyl amine; Methyl vinyl ketone, maleimide, vinylpyridine, vinyl imidazole, vinyl furan, styrene, styrene sulfonate, allyl alcohol and composition thereof.
Wherein preferred especially acrylic acid, methacrylic acid, maleic acid, fumaric acid, .beta.-methylacrylic acid, maleic anhydride and monoesters thereof, acrylic acid methyl ester., methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-butyl acrylate, n-BMA, tert-butyl acrylate, the metering system tert-butyl acrylate, Isobutyl 2-propenoate, isobutyl methacrylate, 2-EHA, N tert butyl acrylamide, the N-octyl acrylamide, acrylic acid 2-hydroxyethyl ester, the acrylic acid hydroxypropyl ester, methacrylic acid 2-hydroxyethyl ester, hydroxypropyl methacrylate, (methyl) acrylic acid alkylidene diol ester, unsaturated sulfonic acid such as acrylamido propane sulfonic acid, vinyl pyrrolidone, caprolactam, vinyl ethers (methyl for example, ethyl, butyl or dodecyl vinyl), vinyl formamide, the vinyl methylacetamide, vinyl amine, the 1-vinyl imidazole, 1-vinyl-glyoxal ethyline, methacrylic acid N, N-dimethylamino methyl ester and N-[3-(dimethylamino) propyl group] Methacrylamide; Chlorination 3-methyl isophthalic acid-vinyl imidazole, 3-methyl isophthalic acid-vinyl imidazole Methylsulfate, methacrylic acid N, the N-dimethylaminoethyl is with chloromethanes, Methylsulfate or the quaternised N-[3-of sulphuric acid diethyl ester (dimethylamino) propyl group] Methacrylamide.
In embodiment very particularly preferably, the monomer that uses (a) as the acrylic acid tertiary butyl ester (=a1) and methacrylic acid (=a2).
The monomer that contains basic nitrogen atom here can be quaternized as follows:
For making amine quaternized, in alkyl, have the alkyl halide of 1 to 24 carbon atom such as chloromethanes, Celfume, iodomethane, ethyl chloride, bromoethane, chloropropane, chlorohexane, chlorinated dodecane, lauryl chloride, with benzyl halogenide, particularly benzyl chloride and benzyl bromide a-bromotoluene be suitable.Other suitable quaternizing agents are sulphuric acid dialkyl, particularly dimethyl sulfate or dithyl sulfate.The quaternized also available alkylene oxide of basic amine such as oxirane or expoxy propane carry out in the presence of acid.Preferred quaternizing agent is chloromethanes, dimethyl sulfate or dithyl sulfate.
In preferred embodiments, the monomer of use (a) is (methyl) acrylate.
Quaternized can carrying out before polymerization or after the polymerization.
In addition, can use the product (R of the quaternized chloropropylene oxide of acid of unsaturated acids such as acrylic or methacrylic and logical formula V 18=C1 to C40 alkyl).
Figure A0081209900271
Its example is (methyl) acryloxy hydroxypropyl-trimethyl ammonium chloride and (methyl) acryloxy hydroxypropyl triethyl ammonium chloride.
The alkalescence monomer also can pass through it is used mineral acid such as sulphuric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, phosphoric acid or nitric acid, or neutralizes and cationization with organic acid such as formic acid, acetic acid, lactic acid or citric acid.
Except above-mentioned monomer, can also use macromonomer to contain the polysiloxanes macromonomer, or Wan oxazolin macromonomer is as monomer, as describing among the EP 408 311 as what contain one or more free redical polymerization groups.
In addition, can also make up or use fluorochemical monomer (as describing among the EP558423) separately, or have crosslinked action or regulate the chemical compound of molecular weight.
Spendable regulator is the chemical compound that those skilled in the art habitually practise, as sulphur compound (for example mercaptoethanol, 2-ethylhexyl mercaptoacetate, TGA or lauryl mercaptan) and three bromochloromethanes or other chemical compound of the molecular weight of gained addition polymers being had regulating action.If suitable, can also use the polysiloxane compound that contains mercaptan.The no polysiloxanes regulator of preferred use.
Spendable cross-linking monomer is the chemical compound with at least two ethylenical unsaturated double bonds, as the ester of ethylenically unsaturated carboxylic acids such as acrylic or methacrylic acid and polyhydric alcohol, the ether of at least a dihydroxylic alcohols such as vinyl ethers or allyl ether.Same suitable be straight or branched, linearity or cyclic aliphatic or aromatic hydrocarbon with at least two two keys, wherein for aliphatic hydrocarbon conjugation not.The amide of acrylic acid and methacrylic acid and at least a two functional amines' N-allyl amine such as 1 and 1,3-diaminopropanes also are suitable.Same suitable is triallylamine or corresponding ammonium salt, N-vinyl compound or urea derivative, at least a difunctionality amide, cyanurate or carbamate (Urethanen).Other suitable crosslinking agent is divinyl diox, tetraallyl silane or tetrem thiazolinyl silane.
Particularly preferred cross-linking agent is for example methylene-bisacrylamide, triallylamine and triallyl ammonium, divinyl imidazoles, N, the product of N '-divinyl ethylidene-urea, polyhydric alcohol and acrylic or methacrylic acid, polyalkylene oxide or with the methacrylate and the acrylate of the polyhydric alcohol of oxirane and/or expoxy propane and/or chloropropylene oxide reaction.
Monomer of the present invention (a) if contain ionizable group, then partially or completely neutralizes with acid or alkali before polymerization or after the polymerization, so that for example water solublity or water dispersible are adjusted to required level.
Spendable being used to is for example inorganic base such as sodium carbonate, alkali metal hydroxide and ammonia with the monomeric nertralizer of acidic group, organic base such as amino alcohol, be specially 2-amino-2-methyl-1-propanol, monoethanolamine, diethanolamine, triethanolamine, triisopropanolamine, three [(2-hydroxyl)-1-propyl group] amine, 2-amino-2-methyl-1, ammediol, 2-amino-2-methylol-1, ammediol and diamidogen such as lysine.
The spendable monomeric nertralizer that is used to cationizable groups is for example mineral acid example hydrochloric acid, sulphuric acid or phosphoric acid and organic acid such as carboxylic acid, lactic acid, citric acid etc.
The specially suitable polyorganosiloxane ramification (b) that contains polyalkylene oxide is to contain those of following construction unit:
Figure A0081209900281
Wherein: R 2=CH 3Or
Figure A0081209900282
R 3=CH 3Or R 2R 4=H, CH 3,
Figure A0081209900284
R 6For can containing the organic group with 1 to 40 carbon atom of amino, carboxylic acid or sulfonate ester group, or, be the anion of mineral acid for C=O,
Radicals R wherein 1Can be identical or different, and,, be aromatic hydrocarbon group for having the cyclic aliphatic hydrocarbon of 3 to 20 carbon atoms derived from aliphatic hydrocarbyl with 1 to 20 carbon atom, or and R 5Identical, wherein:
Figure A0081209900291
Condition is a radicals R 1, R 2Or R 3In at least one be the group that contains polyalkylene oxide defined above,
With n be 1 to 6 integer,
X and y are that to make the molecular weight of polysiloxane block be 300 to 30,000 integer,
A, b can be the integer between 0 to 50, condition be a and b sum greater than 0 and c be 0 or 1.
Preferred radicals R 2And R 5For summation a+b wherein is those groups of 5 to 30.
Radicals R 1Be preferably selected from following group: methyl, ethyl, propyl group, butyl, isobutyl group, amyl group, isopentyl, hexyl, octyl group, decyl, dodecyl and octadecyl, cycloaliphatic groups, be specially cyclohexyl, aromatic group, be specially phenyl or naphthyl, mix aromatic-aliphatic group such as benzyl or phenethyl, and tolyl and xylyl and R 5
Specially suitable radicals R 4For wherein working as R 4=-(CO) c-R 6The time, R 6For having 1 to 40 carbon atom and can further having ion source group such as NH 2, COOH and SO 3Those of the alkyl of H, cycloalkyl or aryl.
Preferred inorganic group R 6When C=O phosphate radical and sulfate radical.
In particularly preferred embodiment of the present invention, with the chemical compound of following general formula as the polyorganosiloxane ramification (b) that contains polyalkylene oxide:
Figure A0081209900292
R wherein 1=-CH 3
R 4=-H ,-COCH 3, C 1-C 4Alkyl
N=1 to 6, particularly 2 to 4, preferred 3
X and y are that to make the molecular weight of polysiloxane block be 1000 to 5000 integer,
A, b can be the integer between 0 to 50, and condition is that a and b sum are greater than 0.
These particularly preferred polyorganosiloxane ramifications are known with CAS No.872 44-72-2.Commercial product is with trade name Belsil DMC 6031 TM(Wacker), Dabco DC193, Dabco DC 5357, Dow Corning 198 TM, Dow Corning 5039 TMAnd Silwet7600 TM(Witco) those of Huo Deing.
These particularly preferred polyorganosiloxane ramifications are known with CAS No.71965-38-3.Commercial product is those that obtain with trade name Abil B 8842, Abil B 8843, Silwet L 7607 (Witco).
Particularly preferably be equally with trade name Belsil DMC 6032 TM(Wacker) and Dow Corning 190 TMThose polyorganosiloxane ramifications that (Dow Chemicals) buys.
The monomer (a) that contains polysiloxane polymer of the present invention can constitute 50 to 99.9wt%, and preferred 70 to 99wt%, and preferred especially 85 to 98wt%.If the mixture of ethylenically unsaturated monomer (a) with two kinds of monomers (a1 and a2) used, proved that then it is favourable using 49.5 to 99wt% (a1) and 0.5 to 40wt% (a2).
Polyorganosiloxane ramification (b) is usually with 0.1 to 50wt%, and preferred 0.5 to 20wt%, and preferred especially 2 to 15wt% amount is present in the addition polymers of the present invention.
In particularly preferred embodiments, the polymer that can the monomer mixture by the following component of radical polymerization obtains of use:
(a1) (methyl) acrylate, particularly tert-butyl acrylate of 49.5 to 99wt%
(a2) another of 0.5 to 40wt% (methyl) acrylate, particularly methacrylic acid
(b) polyorganosiloxane ramification that contains polyalkylene oxide of 0.5 to 20wt% following general formula
Figure A0081209900311
R wherein 1=-CH 3
R 4=-H ,-COCH 3, C 1-C 4Alkyl
N=1 to 6, particularly 2 to 4, preferred 3
X and y are that to make the molecular weight of polysiloxane block be 1000 to 5000 integer,
A, b can be the integer between 0 to 50, and condition is that a and b sum are greater than 0.
If polysiloxane compound (b) does not exist between polymerization period, but sneak into after polymerization, then obtain very softish adhesive membrane usually, this thin film is not suitable in skin and the cosmetic hair according to the present invention.
This shows the possible grafting that addition polymers and polysiloxane compound can take place between polymerization period, help good film properties, as inviscid, high surface flatness and hardness and improved block intensity.Yet, also can expect yet polymer of the present invention can obtain grafted mechanism of being different from of its advantageous property.
Term " polymerizable " is meant that the monomer of use can be with any conventional synthetic method polymerization.
For example, this can be polymerisation in solution, emulsion polymerisation, reverse emulsion polymerization, suspension polymerisation, inverse suspension polymerization or precipitation polymerization, to spendable method and unrestricted.In polymerisation in solution, water, habitual organic solvent or polyorganosiloxane ramification of the present invention itself can be used as solvent.
The K value that polymer of the present invention preferably has (according to Fickentscher, Cellulosechemie, Vol.13, pp.58-64 (1932) is measuring 0.15% concentration solution in the 0.5M sodium chloride solution under 250 ℃) and be 30 to 50, preferred 37 to 41.
Specially suitable polymer be water soluble or its water dispersible enough big so that its with greater than 0.1g/l, the amount that is preferably greater than 0.2g/l is water-soluble: those of ethanol=20: 80 (% (volume): % (volume)) solvent mixture.
For the present invention, " water dispersible " polymer is those polymer that formed fluid and with the naked eye can not detect solid particle therein when contacting with water in 24 hours under no optics instrument.Whether for detecting polymer is water dispersible, adds in 100ml water (20 ℃) with the thick form of film of 100 μ m the 100mg addition polymers and jolting 24 hours on commercial jolting device platform.If after the jolting, no longer observe solid particle, but the fluid muddiness, then addition polymers is a water dispersible; When not having muddiness, be called water miscible.
During monomer polymerization,, also can there be other polymer, as homopolymerization and copolymer and polyamide, polyurethane or the polyester of ethylenically unsaturated monomer if suitable.Polyamide, polyurethane, polyester preferably carry out ion modification with for example carboxylate or sulfonate groups.
According to the present invention, particularly preferred polymer is for example with trade name Luviflex TMSilk (INCI title: PEG/PPG-25/25 polydimethylsiloxane/acrylate/tert-butyl acrylate; BASF Aktiengesellschaft) polymer of Gou Maiing.
Preparation of the present invention can water or water-alcohol solution, the O/W and the W/O emulsion of shampoo, Emulsion (Cremes), foam, washing liquid, mousse (Mousse), spray (pump spray or aerosol) form, gel or gel spray are present in the final preparation, and correspondingly prepare with other habitual auxiliary agents.
The habitual auxiliary agent of other that can mention is: surfactant, oily matter, emulsifying agent, coemulsifier, greasiness agent ( berfettungsmittel), pearlescent waxes, bodying agent, thickening agent, fat, wax, polysiloxane compound, hydrotropic agent, antiseptic, aromatic oil, dyestuff, stabilizing agent, the pH regulator agent, cosmetics care substance and active ingredient are as AHA acid, fruit acid, ceramide, phytantriol, bisabolol, pantothenylol, collagen, provitamin and vitamin (vitamin A for example, E and C), protein and protein hydrolysate (Semen Tritici aestivi for example, Semen Armeniacae Amarum or Semen Pisi sativi protein), solubilizer, complexant, protective agent, bleach, coloring agent, toner, tanning agent (for example dihydroxy acetone), micro pigment such as titanium dioxide or zinc oxide etc.Can there be polymer in addition.
Suitable anion surfactant is for example alkyl sulfate, alkyl ether sulfate, alkylsulfonate, alkylaryl sulfonate, dialkyl succinylsuccinate salt, salts of alkyl sulfosuccinates salt, N-alkyl sarcosine salt, acyl taurine salt, acyl-hydroxyethyl sulfonate, alkylphosphonic, alkyl ether phosphate, alkyl ether carboxy acid salt, alpha-alkene sulfonate; particularly alkali metal and alkali salt such as sodium, potassium, magnesium, calcium and ammonium salt, and triethanolamine salt.Alkyl ether sulfate, alkyl ether phosphate and alkyl ether carboxy acid salt can have 1 to 10 oxirane or propylene oxide units in molecule, preferred 1 to 3 ethylene oxide unit.
Suitable is for example sodium lauryl sulfate, ammonium lauryl sulfate, sodium laureth sulfate, Zetesol AP, sodium lauryl sarcosinate, oil base sodium succinate, lauryl sulfo-succinic acid ammonium, dodecylbenzene sodium sulfonate, DBSA triethanolamine.
Suitable amphoteric surfactant is for example alkyl betaine, alkyl acyl aminopropyl betanin, alkyl sulfobetaines, glycine alkyl ester, carboxyl glycine alkyl ester, alkyl both sexes acetate (amphoacetate) or propionate, alkyl both sexes diacetin (amphodiacetate) or dipropionate.
For example, can use Cortex cocois radicis dimethyl methyl CAB, lauryl betaine, Cortex cocois radicis acylamino-(cocamido) CAB or Cortex cocois radicis both sexes sodium propionate (Natrium-cocamphopropionat).
Suitable non-ionic surface active agent is for for example aliphatic alcohol or have the product of alkyl phenol and the oxirane and/or the expoxy propane of 6 to 20 carbon atoms in the alkyl chain that can be linearity or branching.The amount of alkylene oxide is that every mol alcohol about 6 is to 60mol.Same suitable be alkyl amine oxide, list-or fatty acid ester, ethoxylated fatty acid amide, alkyl poly glucoside or the sorbitan ether-ether of dialkyl group alkanolamide, Polyethylene Glycol.
In addition, these compositionss can comprise habitual cationic surfactant, as quaternary ammonium compound (for example hexadecyltrimethylammonium chloride).
Compositions of the present invention, the particularly compositions of shampoo batching form generally include as the anion surfactant of surface of base activating agent and as the both sexes and the non-ionic surface active agent of cosurfactant.
These compositionss generally include 2 to 50wt%, and preferred 5 to 40wt%, preferred especially 8 to 30wt% surfactant.
Suitable oily matter is for example based on the Guerbet alcohol of the aliphatic alcohol with 6 to 18 carbon atoms, preferred 8 to 10 carbon atoms, linear C 6-C 22-fatty acid and linear C 6-C 22The ester of-aliphatic alcohol, branching C 6-C 13-carboxylic acid and linear C 6-C 22The ester of-aliphatic alcohol, linear C 6-C 22The ester of-fatty acid and branching alcohol, particularly 2-Ethylhexyl Alcohol, hydroxy carboxylic acid and linearity or branching C 6-C 22The ester of-aliphatic alcohol, particularly malic acid dioctyl ester, the ester of linearity and/or branching fatty acid and polyhydric alcohol (as propylene glycol, glycol dimer or triol trimer) and/or Guerbet alcohol is based on C 6-C 10The triglyceride of fatty acid is based on C 6-C 18Liquid glycerol list/two/three esters of fatty acid, C 6-C 22-aliphatic alcohol and/or Guerbet alcohol and aromatic carboxylic acid, particularly benzoic ester, vegetable oil, branched primary alcohol, substituted cyclohexane, linear and branching C 6-C 22-aliphatic alcohol carbonic ester, Guerbet carbonic ester, benzoic acid and linearity and/or branching C 6-C 22The ester of-alcohol (Finsolv for example? TN), each alkyl has the symmetry or the asymmetric dialkyl ether of the linearity or the branching of 6 to 22 carbon atoms, epoxidized fatty acid ester and many pure open loop products, silicone oil and/or aliphatic series or cycloalkane.
Suitable oily matter is a vegetable and animals oils, as Oleum helianthi, Oleum Cocois, American Avocado Tree oil, olive oil or lanoline.
Suitable emulsifying agent is for for example being selected from non-ionic surface active agent at least a in following group:
(1) 2 to 30mol oxirane and/or 0 to 5mol expoxy propane on the linear aliphatic alcohol with 8 to 22 carbon atoms, have on the fatty acid of 12 to 22 carbon atoms and have addition compound product on the alkylphenol of 8 to 15 carbon atoms at moieties;
(2) 1 C to the addition compound product of 30mol oxirane on glycerol 12/18-fatty acid list-diester;
(3) have the saturated and unsaturated fatty acid of 6 to 22 carbon atoms and the glycerol list-diester and the sorbitan list-diester of oxirane additive product thereof;
(4) in alkyl, have alkyl list and the oligoglycosides and the ethoxylation analog thereof of 8 to 22 carbon atoms;
(5) 15 to the addition compound product of 60mol oxirane on Oleum Ricini and/or castor oil hydrogenated;
The ester of (6) polyol esters, particularly polyglycereol is as poly-castor oil acid polyglycerin ester, poly--12-hydroxy stearic acid polyglycerin ester or polyglycereol two polyester.Same suitable is the mixture of two or more chemical compounds in this class material;
(7) 2 to the addition compound product of 15mol oxirane on Oleum Ricini and/or castor oil hydrogenated;
(8) based on linearity, branching, saturated or unsaturated C 6/22The part ester of-fatty acid, castor oil acid and 12-hydroxy stearic acid and glycerol, polyglycereol, tetramethylolmethane, dipentaerythritol, sugar alcohol (as Sorbitol), alkyl androstanediol (as methyl glucosamine, butyl glucoside, lauryl glucoside) and polyglucoside (for example cellulose);
(9) mono phosphoric acid ester, two and the trialkyl ester, and mono phosphoric acid ester-, two-and/or three-PEG-Arrcostab and salt thereof;
(10) wool wax alcohol;
(11) poly-alkyl, polyether copolymer of polysiloxanes and corresponding derivant;
(12), and/or have the fatty acid, methyl glucoside of 6 to 22 carbon atoms and alcohol how according to the mixed ester of tetramethylolmethane, fatty acid, citric acid and the aliphatic alcohol of Deutsche Bundespatent 1165574, the mixed ester of preferably glycerine or polyglycereol and
(13) poly alkylene glycol.
Oxirane and/or the expoxy propane addition compound product on the glycerol list of aliphatic alcohol, fatty acid, alkyl phenol, fatty acid and diester and sorbitan list and diester or on Oleum Ricini is known commercial product.They are homologue mixtures, and its alkoxylate average degree is equivalent to the amount of oxirane and/or expoxy propane and carries out the ratio of the substrate of additive reaction with it.The C of the addition compound product of oxirane on glycerol 12/18-fatty acid list and diester be known R ü ckfettungsmittel as cosmetic formulations in Deutsche Bundespatent 2024051.C 8/18-alkyl list and oligoglycosides, Its Preparation Method And Use are well known in the prior art.Its preparation is reacted with the primary alconol with 8 to 18 carbon atoms by glucose or oligosaccharide especially and is carried out.For glucosides ester, wherein ring-type glycosyl group and the monoglycosides of aliphatic alcohol with glucosides form bonding, and the oligoglycosides of oligomeric degree preferred about at the most 8 is suitable.Oligomeric degree is the assembly average for distributing based on the homologue that is customarily used in these type of industrial products here.
The emulsifying agent that uses also can be zwitterionic surfactant.The term zwitterionic surfactant is used in reference to those surface active cpds that have at least one quaternary ammonium group and at least one carboxylate radical and a sulfonate radical in molecule.Specially suitable zwitterionic surfactant is so-called betanin; as glycine N-alkyl-N; the N-Dimethyl Ammonium; as glycine Cortex cocois radicis alkyl dimethyl ammonium; glycine N-acylamino-propyl group-N, the N-Dimethyl Ammonium is as glycine Cortex cocois radicis acylamino-propyl-dimethyl ammonium; with 2-alkyl 3-carboxymethyl 3-hydroxyethyl imidazole quinoline that in alkyl or acyl group, has 8 to 18 carbon atoms under each situation and hydroxyethyl-carboxymethyl glycine Cortex cocois radicis acylamino-ethyl ester.Particularly preferably be with the known fatty acid amide derivant of CTFA title AMPHORAM C30.Same suitable emulsifying agent is an amphoteric surfactant.Amphoteric surfactant is interpreted as being meant the C that removes in the molecule 8/18Outside-alkyl or the acyl group, also contain at least one free amine group and at least one COOH or SO 3H group and can form those surfactants of inner salt.The example of suitable amphoteric surfactant is N-alkyl glycine, N-alkyl propanoic acid, N-alkylamino butanoic acid, N-alkyl imino dipropionic acid, N-ethoxy-N-alkyl acyl aminopropyl glycine, N-alkyl taurine, N-alkyl sarcosine, 2-alkylamino propanoic acid and has the alkylamino acetic acid of about 8 to 18 carbon atoms under each situation in alkyl.Particularly preferred amphoteric surfactant is N-Cortex cocois radicis alkylamino propionate, Cortex cocois radicis acylamino-ethylamino propionate and C 12/18-acyl group sarcosine.Except that amphoteric emulsifier, the quaternary ammonium emulsifying agent also is suitable, four esters (Esterquat) class wherein, and the quaternized difatty acid triethanolamine ester salts of preferable methyl is particularly preferred.
As the greasiness agent, can use material such as lanoline and lecithin, and polyethoxylated or acyl group lanoline and lecithin derivant, many alcohol fatty acid esters, monoglyceride and Marlamid, the latter also plays the effect of foam stabiliser.
The example of suitable pearlescent waxes is: alkylidene diol ester is specially glycol distearate; Marlamid is specially the coconut fatty acid diglycollic amide; Partial glyceride is specially the stearic acid monoglyceride; The ester of the polybasic carboxylic acid that optional hydroxyl replaces and the aliphatic alcohol of 6 to 22 carbon atoms is specially tartaric long-chain ester; Lipoid material, as aliphatic alcohol, aliphatic ketone, fatty aldehyde, aliphatic ether and aliphatic carbonate ester (having at least 24 carbon atoms altogether) are specially laurone and distearyl ether; Fatty acid, as stearic acid, hydroxy stearic acid Huo behenic acid, the olefin epoxide with 12 to 22 carbon atoms with have the aliphatic alcohol of 12 to 22 carbon atoms and/or have open-loop products and its mixture of the polyhydric alcohol of 2 to 15 carbon atoms and 2 to 10 hydroxyls.
Suitable bodying agent mainly is to have 12 to 22, the aliphatic alcohol or the hydroxy fatty alcohols of preferred 16 to 18 carbon atoms, and partial glyceride, fatty acid or hydroxy fatty acid.The mixture of the oligomeric alkyl glucoside of preferred these materials and same chain length and/or fatty acid N-methyl glucose amide and/or poly--12-hydroxy stearic acid polyglycerin ester.Suitable thickening is for example polysaccharide, xanthan gum particularly, guar gum, agaropectin, alginate and Tyloses, cellulose derivative, for example carboxymethyl cellulose and hydroxyethyl-cellulose, and the higher molecular weight polyethyleneglycol of fatty acid-and diester, polyacrylate is (for example available from the Carbopols of Goodrich TMOr available from the Synthalens of Sigma TM), polyacrylamide, polyvinyl alcohol and polyvinylpyrrolidone, surfactant, as ethoxylated fatty acid glyceride, fatty acid and the ester of many alcohol as tetramethylolmethane or trimethylolpropane have alcohol ethoxylate or oligomeric alkyl glucoside that narrow homologue distributes, and electrolyte, as sodium chloride and ammonium chloride.
The exemplary of fat is a glyceride, and suitable wax especially be Cera Flava, Brazil wax, and candelilla wax, montan wax, paraffin or microwax are chosen wantonly with hydrophilic wax such as cetyl stearyl alcohol or partial glyceride and are mixed.Spendable stabilizing agent is the slaine of fatty acid, as the stearate or the ricinate of magnesium, aluminum and/or zinc.
Suitable polysiloxane compound is for example dimethyl polysiloxane, methyl phenyl silicone, cyclic polysiloxanes, and amino-, fatty acid-, alcohol-, polyethers-, epoxy-, fluoro-, glucosides-and/or the polysiloxane compound of alkyl-modification, it at room temperature can be liquid or resin form.The exemplary of fat is a glyceride, and suitable wax especially be Cera Flava, Brazil wax, and candelilla wax, montan wax, paraffin or microwax are chosen wantonly with hydrophilic wax such as cetyl stearyl alcohol or partial glyceride and are mixed.Spendable stabilizing agent is the slaine of fatty acid, as magnesium stearate, aluminium stearate and/or zinc stearate.
Suitable solvent is in particular water and has rudimentary single pure or many alcohol of 1 to 6 carbon atom and composition thereof; Preferred single alcohol or many alcohol are ethanol, isopropyl alcohol, propylene glycol, glycerol and sorbitol.
For improving mobile performance, also can use hydrotropic agent, as ethanol, isopropyl alcohol or how pure.Here suitable many alcohol preferably have 2 to 15 carbon atoms and at least two hydroxyls.Typical example is:
-glycerol;
-aklylene glycol is ethylene glycol for example, diethylene glycol, and propylene glycol, butanediol, hexanediol and mean molecule quantity are 100 to 1000 daltonian Polyethylene Glycol; From condensation degree is 1.5 to 10 the oligomeric glycerol mixture of technical grade, is 40 to 50wt% technical grade diglycerol mixture as diglycerol content;
-methylol compound, for example particularly trimethylolethane, trimethylolpropane, tri hydroxy methyl butane, tetramethylolmethane and dipentaerythritol;
-low alkyl group glucoside particularly has those of 1 to 8 carbon atom in alkyl, as methyl-and butyl glucoside;
-have the sugar alcohol of 5 to 12 carbon atoms, as Sorbitol or mannitol;
-have the sugar of 5 to 12 carbon atoms, as glucose or sucrose;
-amino sugar is as glycosamine.
Suitable examples of preservatives is other class material that part A and B list in phenyl phenol, formalin, metagin, pentanediol or sorbic acid and " cosmetics indication " appendix 6 (Kosmetikverordnung).
These materials comprise all suitable preservatives of the special role that for example has resisting gram-positive bacteria, and for example Triclosan (2,4,4 '-three chloro-2 '-hydroxy diphenyl ether), chlorhexidine (1,1 '-hexylidene two [5-(4-chlorphenyl) biguanide] and TTC (3,4,4 '-the trichlorine carbanilide).Quaternary ammonium compound also is suitable in principle, but is preferred in disinfectant soap and the washing liquid.A lot of spice also have anti-microbial property.The specific mixture that will have special resisting gram-positive bacteria effect is used for the deodorization perfume composition.A large amount of essential oil or its specific components also present significant antibacterial effect as Oleum Caryophylli (eugenol), Oleum menthae (menthol) or thyme oil (thymol).
The working concentration of antiseptic is generally about 0.1 to 0.3wt%.
The aromatic oil that can mention is natural and mixture synthetic perfume.Natural perfume material is the extract of following material: flower (Bulbus Lilii, Garden lavender, Flos Rosae Rugosae, jasmine, orange blossom, the fragrant cananga), stem and leaf (Herba Pelargonii Graveolentis, greenery, Folium citri sinensis), fruit (Fructus Anisi Stellati, coriander, Fructus Foeniculi, Juniperus rigida Sieb.et Zucc.), peel (bergamot, Fructus Citri Limoniae, Citrus), root (Arillus Myristicae, Radix Angelicae Sinensis, Herba Apii graveolentis, Elettaria cardamomum (L.) Maton, Radix Aucklandiae (Radix Vladimiriae), Rhizoma Iridis Tectori, calamus), timber (Masson Pine, sandalwood, guaiaci lignum, Lignum seu Ramulus Cunninghamiae Lanceolatae, rose wood), medicinal herbs and herbage (tarragon, lemon grass (Cymbopogon citratus), Salvia japonica Thunb., Herba thymi vulgaris), needle and branch (PiceameyeriRehd. Et Wils., fir, pinaster, pinon pine), resin and face cream (galbanum, Canarium luzonicum Elemi, Benzoinum, myrrh, Olibanum, opoponax (Opoponax)).Animal material also is suitable as Zibethum and castoreum.Typical synthetic perfume chemical compound is ester, ether, aldehyde, ketone, pure and mild hydrocarbon products.The ester perfume chemical compound be for example acetic acid benzyl ester, phenoxyethyl isobutanoate, acetic acid to tert-butylcyclohexyl ester, acetic acid linalyl ester, acetic acid dimethyl benzyl carbinol ester, acetic acid phenethyl ester, benzoic acid linalyl ester, formic acid benzyl ester, tolyl glycine ethyl ester, cyclohexylpropionic acid allyl ester, styralyl propionate and salicylic acid benzyl ester.Ether comprises for example benzylisoeugenol, aldehyde comprises linear chain alkanal, citral, citronellal, Herba Cymbopogonis Citrari oxy-aldehyde, cyclamen aldehyde, hydroxycitronellal, lilestralis and the Bourgeonat that for example has 8 to 18 carbon atoms, ketone comprises for example ionone, α-different methyl ionone and vertofix coeur, alcohol comprises anethole, citronellol, eugenol, isoeugenol, geraniol, linalool, phenethanol and terpinol, and hydrocarbon mainly comprises terpenes and face cream.Yet preferred use produces the mixture of the different spice of happy fragrance together.The low volatility essential oil that is commonly used for aroma constituent also is suitable as aromatic oil, and the example of these essential oil is sage oil, chamomile oil, Oleum Caryophylli, oil of balm, Oleum menthae, Cortex Cinnamomi leaf oil, limette caul-fat, juniper berry oil, vetiver oil, Olibanum oil, galbanum oil, Labolanum  l and lavandin oil.The preferred oleum bergamottae that uses, dihydromyrcenol, lilestralis, LYRAL, citronellol, phenethanol, jasmonal H, geraniol, benzylacetone, cyclamen aldehyde, linalool, Boisambrene Fort, Ambroxan, indole, MDJ, Sandelice, Fructus Citri Limoniae oil, mandarin oil, tangerine oil, pi-allyl amyl group oxyacetate, Cyclovertal, lavandin oil, Salvia Sclare L.oil, β-damascone, Oleum Pelargonii Graveolentis Bourbon, the salicylic acid cyclohexyl ester, vertofix coeur, Iso-E-Super, FixolideNP, Evernyl, 3-methyl-α-Zi Luolantong, phenylacetic acid, geranyl acetate, the acetic acid benzyl ester, rose oxide, Romillat, Irotyl and Floramat (independent or its mixture).
Spendable dyestuff is allow and material suitable used for cosmetic, for example list in document " Kosmeticsche F  rbemittel " [cosmetics coloring agent], Farbstoffkommissionder Deutschen Forschungsgemeinschaft[Dyes Commission of theGerman Research Council], Verlag Chemie, Weinheim, 1984, pp.81-106.The working concentration of these dyestuffs is generally 0.001 to 0.1wt% by total mixture.
After the polymerization, other polymer can also be added in the polymer formulations of the present invention, depend on definite specific performance.
Other the suitable polymer that is used for this purpose is for example anion, cation, nonionic and neutral polymer.
The example of anionic polymer is homopolymerization-and sodium salt, water solublity or water-dispersible polyester, polyurethane and the polyureas of copolymer and salt thereof, polyhydroxycarboxyliacid acid of acrylic acid and acrylamide.Specially suitable polymer is copolymer (for example, the Luvimer of acrylic acid tertiary butyl ester, ethyl acrylate, methacrylic acid TM100P), the copolymer of ethyl acrylate and methacrylic acid (Luviflex for example TMSoft), N tert butyl acrylamide, ethyl acrylate, acrylic acid copolymer (Ultrahold Strong TM), the copolymer of vinyl acetate .beta.-methylacrylic acid and optional other vinyl esters (Luviset CA66 for example TM), copolymer-maleic anhydride (optional with alcohol reaction), anion polysiloxane, the carboxyl-functional copolymer of vinyl pyrrolidone, tert-butyl acrylate, methacrylic acid for example, acrylic acid and methacrylic acid and hydrophobic monomer are as (methyl) acrylic acid C 4-C 30-Arrcostab, C 4-C 30-alkyl vinyl ester, C 4-C 30-alkyl vinyl ether and hyaluronic copolymer and other are with trade name Amerhold DR-25, Ultrahold TM, Luviset TMP.U.R., Acronal TM, Acudyne TM, Lovocryl TM, Versatyl TM, Amphomer TM(28-4910, LV-71), Placise TML53, Gantrez TMES 425, Adavntage Plus TM, Omnirez TM2000, Resyn TM28-1310, Resyn TM28-2930, Balance TM(0/55), Acudyne TM255, Aristoflex TMA or EastmanAQ TMKnown polymer.
Other other polymer are the cationic polymers that have according to INCI called after polyquaternary amine (Polyquaternium), for example vinyl pyrrolidone/N-vinyl imidazole salt copolymer (Luviquat TMFC, Luviquat TMHM, Luviquat TMMS, Luviquat TMCare), with the quaternised N-vinyl pyrrolidone/copolymer of dimethylaminoethyl methacrylate of dithyl sulfate (Luviquat TMPQ 11), N-caprolactam/N-vinyl pyrrolidone/N-vinyl imidazole salt copolymer (Luviquat TMHold), cationic cellulose derivative (polyquaternary amine-4 and 10), acrylamide copolymer (polyquaternary amine-), Styleeze TMCC-10, Aquaflex TMSF-40 and chitosan derivative.
Other suitable polymers are neutral polymers, as polyvinylpyrrolidone, the copolymer of N-vinyl pyrrolidone and vinyl acetate and/or propionate, polysiloxanes, Vinylcaprolactam homopolymer and with N-vinylpyrrolidone copolymers, polymine and salt thereof, polyvinylamine and salt thereof, cellulose derivative, polyaspartic acid salts and derivant thereof.These comprise with trade name Luviskol TM(K, VA, Plus), PVP K, PVP/VA, Advantage TMHC and the known polymer of H2OLD EP-1.
Same suitable be biopolymer, promptly obtain by the natural reproducible raw material and by the polymer of natural monomeric unit preparation, for example cellulose derivative, chitin, chitosan, DNA, hyaluronic acid and RNA derivant.
Other polymer are betaines polymer, as Yukaformers (R205, SM) and Diaformers.
Following tabulation comprises the INCI/CTFA title and the manufacturer of the polymer of listing above:
????INCI/CTFA Polymer Manufacturer
Acrylate copolymer Amerhold?DR-25 Amerchol
The PVP/VA copolymer Luviskol?VA BASF
The polyethylene caprolactam Luviskol?Plus BASF
Phenylethylene ethylene/propenoic acid ester copolymer Acronal?290?D,296?D BASF
VA/ crotonates copolymer Luviset?CA?66 BASF
Acrylate/acrylamide copolymer Ultrahold?8 BASF
Acrylate/acrylamide copolymer Ultrahold?Strong BASF
Acrylate copolymer Luviflex?Soft BASF
Acrylate copolymer Luvimer?100P,36D,30E BASF
Polyquaternary amine 46 Luviquat?Hold BASF
Polyurethane-1 Luviset?P.U.R. BASF
Methacryl ethyl betanin/acrylate copolymer Diaformer Clariant
Diethylene glycol/CHDM/ isophthalic acid ester/SIP copolymer Eastman?AQ?Polymer Eastman
VA/ crotonates copolymer Aristoflex?A Hoechst?Celanese
Acrylate/diacetone acrylamide copolymer Plascize?L-53 Goo?Chemical
PVP PVP?K ISP
The PVP/VA copolymer PVP/VA ISP
Caprolactam/PVP/ dimethylaminoethyl acrylate methyl amino-ethyl ester copolymer Copolymer VC 713 (=Advantage HC) ISP
Caprolactam/PVP/ dimethylaminoethyl acrylate methyl amino-ethyl ester copolymer H 2OLD EP-1 ISP
PVM/MA butyl ester copolymer Gantrez?ES?425 ISP
VA/ maleic acid butyl ester/isobornyl acrylate Advantage?Plus ISP
The ethyl ester of PVM/MA copolymer Omnirez?2000 ISP
The PVP/DMAPA acrylate copolymer Styleeze?CC-10 ISP
PVP/ caprolactam/DMAPA acrylate copolymer Aquaflex?SF-40 ISP
Yukaformer?R205 ?Mitsubishi
Yukaformer?SM ?Mitsubishi
VA/ crotonates/copolymer Resyn?28-1310 ?National?Starch
VA/ crotonates/neodecanoic acid ester copolymer Resyn?28-2930 ?National?Starch
Octyl acrylamide/acrylate/metering system acid butyl ammonia ethyl ester copolymer Amphomer?28-4910 ?National?Starch
Octyl acrylamide/acrylate/metering system acid butyl ammonia ethyl ester copolymer Amphomer?LV-71 ?National?Starch
Acrylate/octyl acrylamide copolymer Versatyl?42 ?National?Starch
Octyl acrylamide/acrylate copolymer Versatyl?90 ?National?Starch
Acrylate copolymer Balance?0/55 ?National?Starch
Octyl acrylamide/acrylate/metering system acid butyl ammonia ethyl ester copolymer Lovocryl?47 ?National?Starch
Acrylate/hydroxy ester acrylate Acudyne ?Rohm?&?Haas
The total amount of auxiliary agent and additive can be 1 to 50wt%, and preferred 5 to 40wt%, by compositions.
Auxiliary agent can exist between polymerization period and/or add after polymerization.
If polymer of the present invention prepares in cosmetics oil in the inverse suspension polymerization, the oil phase of then choosing according to the present invention is for having the component of good effect (outward appearance, the sensation on skin) to cosmetic ingredients.These components are for example natural oil such as Oleum helianthi, almond oil, American Avocado Tree oil, wax ester such as Jojoba oil, and fatty acid isopropyl esters such as Palmic acid isopropyl esters, myristic acid isopropyl esters, fatty acid glycerine two-and three esters, as caprylic/capric glyceride.The ratio of oil phase in whole emulsion is 15 to 70wt%, and preferred 20 to 35wt%.
For water is scattered in the organic facies, use the W/O emulsifying agent that becomes known for this purpose.The HLB value of the emulsifying agent that uses is 4 to 8[HLB value=hydrophilic, referring to W.C.Griffin, and J.Soc.Cosmet.Chem.1, (1950) 311].These emulsifying agents are the block copolymer and the polyoxyethylene of for example single oleic acid sorbitan ester, monostearate sorbitan ester, glyceryl monostearate, hydroxy fatty acid-polyester.They can total concentration be 2 to 10wt%, and preferred 2 to 5wt% (by total emulsions) are used alone or as a mixture.
Can be that 0.25 to 7wt% (by total emulsion) adds in the emulsion in concentration especially greater than 8 emulsifying agent also with the HLB value.These emulsifying agents are for example ethoxylation C 6-C 12-nonyl phenol and C 12-C 18-aliphatic alcohol, degree of ethoxylation are 5 to 20mol%.
APM is dissolved in the oil phase without any need for special device; Water-containing monomer mutually can be by for example for example using the anchor agitator stirring and emulsifying in the standard polymerization container.The speed of rotation is 30 to 400rpm, the geometry that depends on jar.
After the polymerization, obtain solid content and be 10 to 40wt%, preferred 15 to 35wt% water-in-oil emulsion.For improving solid content, can from emulsion, remove some or all of water by distillation.
Polymer W/O emulsion of the present invention preferably is used as thickening agent in cosmetics for skin or pharmaceutical preparation.Polymer can the W/O emulsion form directly use.At W/O emulsion and the thickening power that gets started the W/O emulsion after cosmetics and/or medicine O/W emulsion are mixed; Needn't add phase transformation agent (Invertierungsmittel) for obtaining optimum efficiency.Can also make the pure aquatic system thickening.So obtain Emulsion gel (Cremegel).
Preparation according to claim 10 and/or 11 is particularly suitable in the cosmetic composition.Therefore, they can be used in the cosmetic composition of cleaning skin for example.These cosmetic cleaning agent are selected from soap bar, as fancy soap, curd soap, transparent soap, high-grade soap, deodorant soap, butterfat soap, baby soap, skin-protection soap, abrasive soap and synthetic detergent, liquid soap such as pulpous state soap, soft soap and washing pastel, liquid detergent, the shower preparation is as washing liquid, shower preparation and gel, foam bath, oil bath and detergent compositions and the foam of having a shave, washing liquid and Emulsion.
Preparation of the present invention also can be used in the cosmetic formulations of skin nursing.Skin care compositions and methods is in particular W/O or O/W skin cream, daily and ight Emulsion, eye Emulsion, face Emulsion, crease-resistant Emulsion, moistening Emulsion, bleaching Emulsion, vitamin Emulsion, skin lotion, nursing washing liquid and moisturizing emulsions form.
In addition, they are applicable to cosmetics for skin preparation such as facial nourishing agent (Gesichtswasser), facial film, deodorizer and other cosmetics washing liquid.
In addition, preparation of the present invention can be used as pore cleaning or skin foaming bar, is used for anti-acne products, protective agent, the product of having a shave, depilatory, personal hygiene products, footcare product and be used for children's's nursing.
Novel formulation according to claim 10 and/or 11 is specially adapted in the cosmetic hair, is preferred for preparation such as hair-care agent, shampoo, hair abluent, suppurative mastitis, the liquid of making a start (Spitzenfluid), permanent hair-waving with in nertralizer, hot oil processing preparation, regulator, curly hair relaxant, moulding circumvolution washing liquid (Festigerlotionen), typing washing liquid, shampoo, hair dye or the hair spray.
When preparation during hair setting composition, what must consider is to diffuse to environmental legislation in the atmosphere, the content of the pure and mild volatilizer of therefore necessary reduction owing to relate to control VOC (VOC).
Preparation of the present invention is preferably used as film former and/or the coating materials in cosmetics and/or the pharmaceutical preparation, especially for containing keratin and similar keratic surface, in hair, skin and fingernail.
In particularly preferred embodiments, will be used for the cosmetic formulations of manicure according to the preparation of claim 10 and/or 11.
Very particularly preferably be the purposes of preparation in decorative cosmetic preparations according to claim 10 and/or 11.
The present invention further provides the purposes of polymer in decorative cosmetic preparations, described polymer can obtain by the monomer mixture of the following component of radical polymerization:
(a1) (methyl) acrylate, particularly tert-butyl acrylate of 49.5 to 99wt%
(a2) another of 0.5 to 40wt% (methyl) acrylate, particularly methacrylic acid
(b) polyorganosiloxane ramification that contains polyalkylene oxide of 0.5 to 20wt% following general formula
Figure A0081209900441
R wherein 1=-CH 3
Figure A0081209900442
R 4=-H ,-COCH 3, C 1-C 4Alkyl n=1 to 6, particularly 2 to 4, preferred 3
X and y are that to make the molecular weight of polysiloxane block be 1000 to 5000 integer,
A, b can be the integer between 0 to 50, and condition is that a and b sum are greater than 0.
The decorative cosmetic preparations that can mention is for for example hiding eyebrow pencil, stage cosmetics, mascara (Mascara) and eye shadow, lipstick, kohl eyebrow pencil (Kajalstifte), eyeliner (Eyeliner), cosmetics, foundation cream, kermes (Rouges) and powder and eyebrow pencil (Augenbrauenstiften), particularly nial polish (Nagellacke).
The amount of polymer of the present invention in cosmetics and/or pharmaceutical preparation is generally 0.001 to 20wt%, and preferred 0.1 to 10wt%, by the total formulation weight amount.
Embodiment 1 to 6: the preparation polymer
With just expecting that 50g raw material 1 and 3.75g raw material 2 are added dropwise to stirring.Then with this mixture heated to 78 ℃.Then in 1.5 hours, be added dropwise to the raw material 1 and the raw material 2 of surplus.This mixture was further stirred 2 hours, in 15 minutes, is added dropwise to raw material 3 then, and with this mixture 78 ℃ of following restir 3 hours.
Embodiment 1
Just expect: 175g ethanol, 7.5g Dow Corning 190 TM
Raw material 1:251g tert-butyl acrylate, 86g methacrylic acid,
37g ethyl acrylate, 75g ethanol
Raw material 2:2g crosses the neopentanoic acid tert-butyl ester, 100g ethanol
Raw material 3:1.5g crosses the neopentanoic acid tert-butyl ester, 57g ethanol
Embodiment 2
Just expect: 175g ethanol, 18.75g Dow Corning 190 TM
Raw material 1:251g tert-butyl acrylate, 86g methacrylic acid,
37g ethyl acrylate, 75g ethanol
Raw material 2:2g crosses the neopentanoic acid tert-butyl ester, 100g ethanol
Raw material 3:1.5g crosses the neopentanoic acid tert-butyl ester, 57g ethanol
Embodiment 3
Just expect: 175g ethanol, 37.5g Dow Corning 190 TM
Raw material 1:251g tert-butyl acrylate, 86g methacrylic acid,
37g ethyl acrylate, 75g ethanol
Raw material 2:2g crosses the neopentanoic acid tert-butyl ester, 100g ethanol
Raw material 3:1.5g crosses the neopentanoic acid tert-butyl ester, 57g ethanol
Embodiment 4
Just expect: 175g ethanol, 18.75g Belsil DMC 6031 TM
Raw material 1:251g tert-butyl acrylate, 86g methacrylic acid,
37g ethyl acrylate, 75g ethanol
Raw material 2:2g crosses the neopentanoic acid tert-butyl ester, 100g ethanol
Raw material 3:1.5g crosses the neopentanoic acid tert-butyl ester, 57g ethanol
Embodiment 5
Just expect: 175g ethanol, 37.5g Belsil DMC 6031 TM
Raw material 1:279g tert-butyl acrylate, 96g methacrylic acid,
75g ethanol
Raw material 2:2g crosses neopentanoic acid butyl ester, 100g ethanol
Raw material 3:1.5g crosses the neopentanoic acid tert-butyl ester, 57g ethanol
Embodiment 6
Just expect: 175g ethanol, 37.5g Belsil DMC 6031 TM
Raw material 1:300g tert-butyl acrylate, 75g methacrylic acid,
75g ethanol
Raw material 2:2g crosses the neopentanoic acid tert-butyl ester, 100g ethanol
Raw material 3:1.5g crosses the neopentanoic acid tert-butyl ester, 57g ethanol
Embodiment 7
The gel batching
Prepare phase A and B mutually separately, and phase B is added among the phase A.
Phase A 0.50wt%Carbopol 980 TM(Goodrich)
The 49.5wt% demineralized water
The 0.40wt% triethanolamine
The polymer of phase B 1.00wt% embodiment 1 or embodiment 5
0.12wt%2-amino-2-methyl propanol
2.00wt%Uvinul?MS?40
20.00wt% ethanol
The 26.48wt% demineralized water
Embodiment 8
Hair cocktail (Haar-Cocktail)
Phase A 3.00wt% Luvigel EM TM(BASF)
2.00wt%?Belsil?DM?1000 TM(Wacker)
2.00wt%?Belsil?CM?1000 TM(Wacker)
1.50wt%?Belsil?PDM?200 TM(Wacker)
1.50wt%?Belsil?ADM?6057?E TM(Wacker)
2.00wt%?Univul?MS?40
0.50wt%?Belsil?DMC?6031 TM(Wacker)
1.00wt% Macadamia Oleum Juglandis (Ex.Huile de
Macadamio is available from Wacker)
0.50wt%?Vitamin-E-Acetat TM(BASF)
1.00wt%?Cremophor?RH?40 TM(BASF)
0.40wt% aromatic oil
Phase B 4.00wt% embodiment 1 or 5 addition polymers
0.46wt% 2-amino-2-methyl propanol
0.10wt%?Euxyl?K?100 TM(Schulke?&?Mayr)
Add 100.00 demineralized waters
Embodiment 9
Similar to Example 8, but with 0.40%Pemulen TR 1 TM(Goodrich) replace 3.00%Luvigel EM TM(BASF)
Add 100.00 demineralized waters
Embodiment 10
Similar to Example 8, but use 3.5%Luvigel EM TMReplace 3.oo%LuvigelEM TM(BASF)
Add 100.00 demineralized waters
Embodiment 11 to 20
Hair spray
Polymer Mixing ratio 8: 2 Mixing ratio 1: 1 Mixing ratio 2: 8
?Luviflex ?Silk/ ?Luviskol ?VA37 ?6.40%Luviflex?Silk ?1.60%Luviskol ?VA37E TM0.74%AMP (2-amino-2-methylpropanol) 51.26% ethanol 40.00%DME (dimethyl ether) ?4.0%Luviflex?Silk ?4.0%Luviskol ?VA37E TM0.46%AMP 51.54% ethanol 40.00%DME ?1.6%Luviflex?Silk ?6.4%Luviskol ?VA37E TM0.19%AMP 51.81% ethanol 40.00%DME
?Luviflex ?Silk/ ?Luviskol ?K30 ?6.4%Luviflex?Silk TM?0.8%Luviskol?K30 TM0.74%AMP 52.06% ethanol 40.0%DME ?4.0%Luviflex?Silk TM?2.0%Luviskol?K30 TM0.46%AMP 53.54% ethanol 40.0%DME ?1.6%Luviflex?Silk TM?3.2%Luviskol?K30 TM0.19%AMP 55.01% ethanol 40.0%DME
?Luviflex ?Silk/ ?Luviskol ?Plus ?6.4%Luviflex?Silk TM?2.0%Luviskol?Plus TM0.74%AMP 50.86% ethanol 40.0%DME ?4.0%Luviflex?Silk TM?5.0%Luviskol?Plus TM0.46%AMP 50.54% ethanol 40.0%DME ?1.6%Luviflex?Silk TM?8.0%Luviskol?Plus TM0.19%AMP 50.21% ethanol 40.0%DME
?Luviflex ?Silk/ ?Luviset ?P.U.R. ?6.4%Luviflex?Silk TM?2.67%Luviset?P.U.R TM0.73%AMP 50.20% ethanol 40.0%DME ?4.0%Luviflex?Silk TM?6.67%Luviset?P.U.R TM0.46%AMP 48.87% ethanol 40.0%DME ?1.6%Luviflex?Silk TM?10.67%Luviset?P.U.R TM0.19%AMP 47.54% ethanol 40.0%DME
?Luviflex ?Silk/ ?Ultrahold ?8 ?6.4%Luviflex?Silk TM?0.8%Ultrahold?8 TM0.82%AMP 51.98% ethanol 40.0%DME ?4.0%Luviflex?Silk TM?2.0%Ultrahold?8 TM0.66%AMP 53.34% ethanol 40.0%DME ?1.6%Luviflex?Silk TM?3.2%Ultrahold?8 TM0.51%AMP 54.69% ethanol 40.0%DME
?Luviflex ?Silk/ ?Ultrahold ?Strong ?6.4%Luviflex?Silk TM?0.8%Ultrahold?Strong TM0.84%AMP 51.96% ethanol 40.0%DME ?4.0%Luviflex?Silk TM?2.0%Ultrahold?Strong TM0.71%AMP 53.29% ethanol 40.0%DME ?1.6%Luviflex?Silk TM?3.2%Ultrahold?Strong TM0.59%AMP 54.61% ethanol 40.0%DME
?Luviflex ?Silk/ ?Luviset ?CA66 ?6.4%Luviflex?Silk TM?0.8%Luviset?CA66 TM0.82%AMP 51.98% ethanol 40.0%DME ?4.0%Luviflex?Silk TM?2.0%Luviset?CA66 TM0.69%AMP 53.31% ethanol 40.0%DME ?1.6%Luviflex?Silk TM?3.2%Luviset?CA66 TM0.53%AMP 54.67% ethanol 40.0%DME
?Luviflex ?Silk/ ?Luviset ?CAN ?6.4%Luviflex?Silk TM?0.8%Luviset?CAN TM0.82%AMP 51.98% ethanol 40.0%DME ?4.0%Luviflex?Silk TM?2.0%Luviset?CAN TM0.70%AMP 53.3% ethanol 40.0%DME ?1.6%Luviflex?Silk TM?3.2%Luviset?CAN TM0.54%AMP 54.66% ethanol 40.0%DME
?Luviflex ?Silk/ ?Amphomer ?6.4%Luviflex?Silk TM?0.8%Amphomer TM0.88%AMP 51.92% ethanol 40.0%DME ?4.0%Luviflex?Silk TM?2.0%Amphomer TM0.83%AMP 52.87% ethanol 40.0%DME ?1.6%Luviflex?Silk TM?3.2%Amphomer TM0.77%AMP 54.43% ethanol 40.0%DME
Embodiment 21 to 30
The hair spray that contains propane/butane 3.5 crust or propane/butane 3.5 crust and adding DME
Polymer Mixing ratio 8: 2 Mixing ratio 1: 1 Mixing ratio 2: 8
?Luviflex ?Silk/ ?Luviskol ?VA37 ?6.40%Luviflex?Silk ?1.60%Luviskol ?VA37E TM0.74%AMP 51.26% ethanol 10.0%Pr/Bu 3.5 (propane/butane 3.5 crust) 30.00%DME ?4.0%Luviflex?Silk ?4.0%Luviskol ?VA37E TM0.46%AMP 51.54% ethanol 10.0%Pr/Bu 3.5 30.00%DME ?1.6%Luviflex?Silk ?6.4%Luviskol ?VA37E TM0.19%AMP 51.81% ethanol 10.0%Pr/Bu 3.5 30.00%DME
?Luviflex ?Silk/ ?Luviskol ?K30 ?6.4%Luviflex?Silk TM?0.8%Luviskol?K30 TM0.74%AMP 52.06% ethanol 40.0%Pr/Bu 3.5 ?4.0%Luviflex?Silk TM?2.0%Luviskol?K30 TM0.46%AMP 53.54% ethanol 40.0%Pr/Bu 3.5 ?1.6%Luviflex?Silk TM?3.2%Luviskol?K30 TM0.19%AMP 55.01% ethanol 40.0%Pr/Bu 3.5
?Luviflex ?Silk/ ?Luviskol ?Plus ?6.4%Luviflex?Silk TM?2.0%Luviskol?Plus TM0.74%AMP 50.86% ethanol 40.0%Pr/Bu 3.5 ?4.0%Luviflex?Silk TM?5.0%Luviskol?Plus TM0.46%AMP 50.54% ethanol 40.0%Pr/Bu 3.5 ?1.6%Luviflex?Silk TM?8.0%Luviskol?Plus TM0.19%AMP 50.21% ethanol 40.0%Pr/Bu 3.5
?Luviflex ?Silk/ ?Luviset ?P.U.R. Impossible ?4.0%Luviflex?Silk TM?6.67%Luviset?P.U.R TM0.46%AMP 48.87% ethanol 10.0%Pr/Bu 3.5 30.00%DME ?1.6%Luviflex?Silk TM?10.67%Luviset?P.U.R TM0.19%AMP 47.54% ethanol 15.0%Pr/Bu 3.5 25.00%DME
?Luviflex ?Silk/ ?Luvimer ?100P ?6.4%Luviflex?Silk TM?0.8%Luvimer?100P TM0.93%AMP 51.87% ethanol 40.0%Pr/Bu 3.5 ?4.0%Luviflex?Silk TM?2.0%Luvimer?100P TM0.94%AMP 53.06% ethanol 40.0%Pr/Bu 3.5 ?1.6%Luviflex?Silk TM?3.2%Luvimer?100P TM0.95%AMP 54.25% ethanol 40.0%Pr/Bu 3.5
?Luviflex ?Silk/ ?Ultrahold ?8 ?6.4%Luviflex?Silk TM?0.8%Ultrahold?8 TM0.82%AMP 51.98% ethanol 40.0%Pr/Bu 3.5 ?4.0%Luviflex?Silk TM?2.0%Ultrahold?8 TM0.66%AMP 53.34% ethanol 40.0%Pr/Bu 3.5 ?1.6%Luviflex?Silk TM?3.2%Ultrahold?8 TM0.51%AMP 54.69% ethanol 40.0%Pr/Bu 3.5
?6.4%Luviflex?Silk TM ?4.0%Luviflex?Silk TM ?1.6%Luviflex?Silk TM
?Luviflex ?Silk/ ?Ultrahold ?Strong ?0.8%Ultrahold?Strong TM0.84%AMP 51.96% ethanol 40.0%Pr/Bu 3.5 ?2.0%Ultrahold?Strong TM0.71%AMP 53.29% ethanol 40.0%Pr/Bu 3.5 ?3.2%Ultrahold?Strong TM0.59%AMP 54.61% ethanol 40.0%Pr/Bu 3.5
?Luviflex ?Silk/ ?Luviset ?CA66 ?6.4%Luviflex?Silk TM?0.8%Luviset?CA66 TM0.82%AMP 51.98% ethanol 10.0%Pr/Bu 3.5 30.0%DME ?4.0%Luviflex?Silk TM?2.0%Luviset?CA66 TM0.69%AMP 53.31% ethanol 10.0%Pr/Bu 3.5 30.0%DME ?1.6%Luviflex?Silk TM?3.2%Luviset?CA66 TM0.53%AMP 54.67% ethanol 10.0%Pr/Bu 3.5 30.0%DME
?Luviflex ?Silk/ ?Luviset ?CAN ?6.4%Luvifkex?Silk TM?0.8%Luviset?CAN TM0.82%AMP 51.98% ethanol 20.0%Pr/Bu 3.5 20.0%DME ?4.0%Luviflex?Silk TM?2.0%Luviset?CAN TM0.70%AMP 53.3% ethanol 20.0%Pr/Bu 3.5 20.0%DME ?1.6%Luviflex?Silk TM?3.2%Luviset?CAN TM0.54%AMP 54.66% ethanol 20.0%Pr/Bu 3.5 20.0%DME
?Luviflex ?Silk/ ?Amphomer ?6.4%Luviflex?Silk TM?0.8%Amphomer TM0.88%AMP 51.92% ethanol 40.0%Pr/Bu 3.5 ?4.0%Luviflex?Silk TM?2.0%Amphomer TM0.83%AMP 52.87% ethanol 40.0%Pr/Bu 3.5 ?1.6%Luviflex?Silk TM?3.2%Amphomer TM0.77%AMP 54.43% ethanol 40.0%Pr/Bu 3.5
Embodiment 31 to 40
The pump spray
Polymer Mixing ratio 8: 2 Mixing ratio 1: 1 Mixing ratio 2: 8
?Luviflex ?Silk/ ?Luviskol ?VA37 ?10.85%Luviflex?Silk ?2.66%Luviskol ?VA37E TM1.27%AMP 85.22% ethanol ?6.74%Luviflex?Silk ?6.66%Luviskol ?VA37E TM0.79%AMP 85.81% ethanol ?2.69%Luviflex?Silk ?10.64%Luviskol ?VA37E TM0.32%AMP 86.35% ethanol
?Luviflex ?Silk/ ?Luviskol ?K30 ?10.85%Luviflex?Silk TM?1.33%Luviskol?K30 TM1.27%AMP 86.55% ethanol ?6.74%Luviflex?Silk TM?3.33%Luviskol?K30 TM0.79%AMP 84.14% ethanol ?2.69%Luviflex?Silk TM?5.32%Luviskol?K30 TM0.32%AMP 83.69% ethanol
?Luviflex ?Silk/ ?Luviskol ?Plus ?10.85%Luviflex?Silk TM?3.33%Luviskol?Plus TM1.27%AMP 84.55% ethanol ?6.74%Luviflex?Silk TM?8.33%Luviskol?Plus TM0.79%AMP 89.14% ethanol ?2.69%Luviflex?Silk TM?13.3%Luviskol?Plus TM0.32%AMP 90.21% ethanol
?Luviflex ?Silk/ ?Luviset ?P.U.R. ?10.85%Luviflex?Silk TM?4.43%Luviset?P.U.R. TM1.27%AMP 83.45% ethanol ?6.74%Luviflex?Silk TM?11.1%Luviset?P.U.R TM0.79%AMP 81.37% ethanol ?2.69%Luviflex?Silk TM?17.73%Luviset?P.U.R TM0.32%AMP 79.26% ethanol
?Luviflex ?Silk/ ?10.85%Luviflex?Silk TM?1.33%Luvimer?100P TM ?6.74%Luviflex?Silk TM?3.33%Luvimer?100P TM ?2.69%Luviflex?Silk TM?5.32%Luvimer?100P TM
?Luvimer ?100P 1.55%AMP 86.27% ethanol 1.56%AMP 88.37% ethanol 1.58%AMP 90.41% ethanol
?Luviflex ?Silk/ ?Ultrahold ?8 ?10.85%Luviflex?Silk TM?1.33%Ultrahold?8 TM1.36%AMP 86.46% ethanol ?6.74%Luviflex?Silk TM?3.33%Ultrahold?8 TM1.1%AMP 88.83% ethanol ?2.69%Luviflex?Silk TM?5.32%Ultrahold?8 TM0.85%AMP 91.14% ethanol
?Luviflex ?Silk/ ?Ultrahold ?Strong ?10.85%Luviflex?Silk TM?1.33%Ultrahold?Strong TM1.4%AMP 86.42% ethanol ?6.74%Luviflex?Silk TM?3.33%Ultrahold?Strong TM1.18%AMP 88.75% ethanol ?2.69%Luviflex?Silk TM?5.32%Ultrahold?Strong TM0.98%AMP 91.01% ethanol
?Luviflex ?Silk/ ?Luviset ?CA66 ?10.85%Luviflex?Silk TM?1.33%Luviset?CA66 TM1.36%AMP 86.46% ethanol ?6.74%Luviflex?Silk TM?3.33%Luviset?CA66 TM1.15%AMP 88.78% ethanol ?2.69%Luviflex?Silk TM?5.32%Luviset?CA66 TM0.88%AMP 91.11% ethanol
?Luviflex ?Silk/ ?Luviset ?CAN ?10.85%Luviflex?Silk TM?1.33%Luviset?CAN TM1.37%AMP 86.45% ethanol ?6.74%Luviflex?Silk TM?3.33%Luviset?CAN TM1.17%AMP 88.76% ethanol ?2.69%Luviflex?Silk TM?5.32%Luviset?CAN TM0.9%AMP 91.09% ethanol
?Luviflex ?Silk/ ?Amphomer ?10.85%Luviflex?Silk TM?1.33%Amphomer TM1.47%AMP 86.35% ethanol ?6.74%Luviflex?Silk TM?3.33%Amphomer TM1.38%AMP 88.55% ethanol ?2.69%Luviflex?Silk TM?3.33%Amphomer TM1.28%AMP 92.7% ethanol
Embodiment 41
Hair spray batching based on dimethyl ether
1.00wt%?Luviskol?K30 TM(BASF)
2.92wt%Luviflex?Silk TM(BASF)
0.92wt%2-amino-2-methyl propanol
The 0.10wt% diisobutyl adipate (Ex.Crodanol DiBA, available from
Croda?Oleochemicals)
The 0.05wt% isodecane
0.10wt% aromatic oil
0.05wt%D-pantothenylol USP TM(BASF)
The 14.78wt% demineralized water
36.08wt% ethanol
The 40.00wt% dimethyl ether
Embodiment 42
Hair spray batching based on iso-butane and pentane
A)6.80%Luviflex?Silk TM(BASF)
0.79%2-amino-2-methyl propanol
14.20% pentane
2.40% normal butane
35.90% iso-butane
39.91% ethanol
B)3.00%Ultrahold?Strong TM(BASF)
1.00%Luviflex?Silk TM(BASF)
0.48%2-amino-2-methyl propanol
0.03%DOW?Corning?190 TM(Dow?Corning)
14.20% pentane
2.40% normal butane
35.90% iso-butane
42.99% ethanol
Embodiment 43
Glazing spraying glue (Glanzspray)
2.00%Luviset?CA66 TM(BASF)
2.00%Luviflex?Silk TM(BASF)
0.46%2-amino-2-methyl propanol
1.00%DOW?Corning?556(Dow?Corning)
0.10% nicotiamide
0.20%D-pantothenylol USP TM(BASF)
14.20% pentane
35.90% normal butane
44.14% ethanol
Embodiment 44
The hair spray VOC80 that contains HFC 152A
2.00%Luviset?CA66 TM(BASF)
4.80%Luviflex?Silk TM(BASF)
0.79%2-amino-2-methyl propanol
56.60% ethanol
15.81% volatilizer 152a (Ex.Dymel 152a is available from DuPont)
20.00% dimethyl ether
Embodiment 45
The hair spray VOC55 that contains vitamin
4.80%Luviflex?Silk TM(BASF)
3.33%Luviset?P.U.R. TM
0.57%2-amino-2-methyl propanol
0.10% nicotiamide (Hoffmann-La Roche)
0.10% pantothenylol USP TM(BASF)
38.83% demineralized water
12.27% ethanol
40.00% dimethyl ether
Embodiment 46
The sun-proof pump spraying glue that is used for hair
2.00%Luviflex?Silk TM(BASF)
0.23%2-amino-2-methyl propanol
2.00%Uvinul MS 40 TM(BASF) (benzophenone-4)
95.77% ethanol
Embodiment 47
The hair renovation agent
1.00%Luviskol?K30 TM(BASF)
4.00%Luviflex?Silk TM(BASF)
0.48%2-amino-2-methyl propanol
0.20% hydrolyzed wheat protein (Ex.Cropesol W TM, available from Croda, Inc.)
0.S0%D-pantothenylol USP TM(BASF)
5.00%1,2-propylene glycol USP TM(BASF)
10.00% ethanol
78.82% demineralized water
Embodiment 48
The glazing gel (Shining Gel) that is used for hair UV protection
Phase A 0.80%Carbopol 2001 ETD TM(Goodrich)
33.84% demineralized water
Phase B 5.00%Abil 200 (Goldschmidt)
3.00%Karion?FP(Merck?KGaA)
3.00%1,2-propylene glycol USP TM(BASF)
1.00%Cremophor?RH40 TM(BASF)
An amount of antiseptic
Phase C 50.00% demineralized water
0.50%Uvinul?P25 TM(BASF)(PEG-25PABA)
2.00%Luviflex?Silk TM(BASF)
0.23%2-amino-2-methyl propanol
Phase D 0.63%2-amino-2-methyl propanol
Embodiment 49
Mascara
Phase A 1.50%Cremophor A 6 TM(BASF)
1.50%Cremophor?A25 TM(BASF)
(Ex.Emersol 120 for 2.00% stearic acid TM, available from Henkel)
3.00%Imwitor?960?K TM(Hüls?AG)
3.00%Softisan?100 TM(Hüls?AG)
1.50%Luvigel?EM TM(BASF)
10.00%Dow?Corning?345 TM(Dow?Corning)
Phase B 4.00%Luviflex Silk TM(BASF)
0.46%2-amino-2-methyl propanol
0.30%Germal?115 TM(Sutton)
72.24% demineralized water
Phase C 0.50% phenyl phenol (Ex.Penoxetol TM,
Available from Nipa-Hardwicke)
Embodiment 50
The shampoo batching
1.50%Luviflex?Silk TM(BASF)
0.17%2-amino-methyl propanol
0.50%Luviskol?K30 TM(BASF)
10.00?Tego-Betaine?L7
40.00%Texapone?NSO
0.10%Euxyl?K100
2.00%NaCl
45.73% water
Embodiment 51
Contain Luviquat Care TMShampoo batching
1.80%Luviflex?Silk TM(BASF)
0.21%2-amino-methyl propanol
0.20%Luviskol?K30 TM(BASF)
7.70%Luviquat?Care TM(BASF)
10.00%Tego-Betaine?L7
40.00%Texapone?NSO
0.10%Euxyl?K100
2.00%NaCl
37.99% water
Embodiment 51
Transparent varnish (Klarlack)
15.0% NC Nitroncellulose
7.0%Luviflex?Silk TM(BASF)
2.4% Camphora
4.5%Palatinol?A
7.0% isopropyl alcohol
8.0% methyl acetate
8.0% ethyl acetate
14.0% acetic acid isopropyl esters
34.1% butyl acetate
Embodiment 52
The transparent varnish of no NC Nitroncellulose
23.0%Luviflex?Silk TM(BASF)
7.0%Ketjenflex?MH
2.4% Camphora
4.5%Palatinol?A
8.0% methyl acetate
8.0% ethyl acetate
14.0% acetic acid isopropyl esters
33.1% butyl acetate
Embodiment 53
VOC 55 hair sprays
21.50% water
35.00% pure SD 40-B
0.95% aminomethyl propanol
8.00%Luviflex TM?Silk
0.20%D, the L-pantothenylol
0.10%Uvinul TMMC 80 (octyl methoxycinnamate)
0.10%Masil TMSF 19 (polydimethylsiloxane Copolyol)
15.00% dimethyl ether
20.00% hydrogen fluorohydrocarbon 152a
Embodiment 54
VOC 55 hair sprays
34.10% water
52.00% pure SD 40-B
0.50% aminomethyl propanol
9.00 Luviset TMP.U.R. (polyurethane-1)
4.00%Luviflex TM?Silk
2.00%D, the L-pantothenylol
0.10%Uvinul TMMC 80 (octyl methoxycinnamate)
0.10%Masil TMSF 19 (dimethicone Copolyol)
Except as otherwise noted, all percentages among the embodiment.
Embodiment 55
In the sterilization spray, be used as film former
150g polymer (embodiment 5) is dissolved in 375 demineralized waters, and adds 375g ethanol.Under agitation (PVP-iodine 30/06 BASFAktiengesellschaft) is dissolved in this polymer solution, and said preparation is transferred in the pump spray bottle with 100g polyvinylpyrrolidone-iodine then.This sterilization spray shows very good film properties on skin, and does not present any iodine loss after stress condition (following 7 days at 52 ℃) is stored down.
Performance
For measuring bending rigidity, prepare the solution of the 3.0wt% concentration of other polymer, polymer of the present invention and preparation (polymer+another polymer).
Bending rigidity is measured 5 to 10 hair tow (the about 3g of à, 24cm is long) under 20 ℃ and 65% relative humidity.
The dry hair tow that takes by weighing is immersed in the polymer solution of 3% concentration, by flooding and taking out three times and guarantee uniform distribution.
Excessive film former solution is extruded between thumb and forefinger, then with the careful extruding of hair tow by extruding between filter paper.Then, make them have circular cross section with the hands molding of hair tow.With they under 20 ℃ and 65% relative humidity in biotron dried overnight.
These tests are carried out with stretching/compressing tester under 20 ℃ and 65% relative humidity in biotron.
Hair tow symmetry is positioned over two cylindrical rollers that are used for the sample insertion.Use the circular hole boring machine with the just bending (polymeric film fracture) above the center of this tow then.Measure its required power and provide with weighing unit (50N) with newton.
Table 1 provides the bending rigidity of each polymer and the preparation of the present invention in alcoholic solution (comprises and changed weight ratio (2: 8; 1: 1; 8: 2) addition polymers and another polymer) bending rigidity.The polymer that uses is Luviflex Silk TM(BASF), its bending rigidity is 109cN.
Table 1: the bending rigidity cN (3wt%w.s. in dehydrated alcohol; 20 ℃ and 65% relative humidity)
Polymer only ??Luviflex?Silk TMWith the ratio of polymer 2: 81: 18: 2
?Luviskol?VA?37?E ????80cN ????90 ????95 ????106
?Luviset?CAN ????125cN ????129 ????133 ????108
?Ultrahold?8 ????80cN ????90 ????97 ????110
?Luviskol?Plus ????105cN ????120 ????117 ????116
Bending rigidity and the preparation of the present invention in VOC 80 batchings that table 2 provides each polymer (comprise and changed weight ratio (2: 8; 1: 1; 8: 2) polymer and another polymer) bending rigidity.The polymer that uses is Luviflex Silk TM(BASF), its bending rigidity in VOC 80 batchings is 120cN.
Table 2: the bending rigidity cN (3wt%w.s. in VOC 80; 20 ℃ and 65% relative humidity)
Polymer only Luviflex?Silk TMWith the ratio of polymer 2: 81: 18: 2
?Luviskol?VA?37?E ????109cN ????137 ????132 ????114
?Luviset?CA?66 ????112cN ????159 ????123 ????117
?Ultrahold?Strong ????180cN ????166 ????169 ????140
?Luviskol?Plus ????129cN ????172 ????150 ????126
?Luviset?P.U.R. ????168cN ????188 ????166 ????140
?Amphomer ????166cN ????172 ????152 ????175
Clear find out that from table 1 and 2 bending rigidity of preparation of the present invention is obviously greater than the bending rigidity sum of each polymer in alcoholic solution and VOC 80 batchings.
For measuring curling conservation rate, the concentration of preparation polymer, addition polymers and preparation of the present invention (polymer+another polymer) is the solution of 1.8wt%.Used comparative sample is one another polymer or polymer under the various situations.Preparation of the present invention is with weight ratio 8: 2,1: 1 and preparation in 2: 8.
Curl conservation rate by following measurement
The dry hair tow of washing was being placed 15 minutes in 50% concentration ethanol (dehydrated alcohol/distilled water 1: 1) under about 40 ℃.
Excessive liquid is extruded between thumb and forefinger, and the hair tow is twined around lucite tube.Then with the hair tow 65 to 70 ℃ of following dried overnight.
After at room temperature 15 minutes, hair is launched.At the rotation about 5g hair spray (about certainly 20cm place) of spraying thereon in the topknot.Place it under the room temperature dry 1 hour then.
Topknot one end is hung and measures the length (LO) of topknot.This topknot is positioned in the weather control chamber (25 ℃, 90% relative humidity), and at 15,30,60 and 90 minutes, and measure its length (Lt) after 2,3,4,5 and 24 hours.Test is at least 5 hairline Shu Jinhang.
Crooked conservation rate %=[(L-Lt)/(L-LO)] * 100
L=hair lengths (15.5cm)
The dried hair lengths of LO=
The hair lengths of Lt=after handling under the weather controlled condition
Table 3 provides the curling conservation rate of each polymer and the preparation of the present invention in ethanol (comprises and changed weight ratio (2: 8; 1: 1; 8: 2) addition polymers and another polymer) curling conservation rate.The polymer that uses is Luviflex Silk TM(BASF), its curling conservation rate is 93%.
Table 3: the conservation rate % (1.8wt%w.s. in dehydrated alcohol curls; 25 ℃ and 90% relative humidity)
Polymer only Luviflex?Silk TMWith the ratio of polymer 2: 81: 18: 2
?Luviskol?VA?37?E ????20% ????34 ????74 ????82
?Luviskol?K?30 ????<20% ????25 ????70 ????84
?Luviset?CAN ????60% ????77 ????88 ????84
?Luviset?CA?66 ????20% ????65 ????75 ????70
Table 4 provides fully, and the curling conservation rate and the preparation of the present invention in VOC 80 batchings of polymer (comprise and changed weight ratio (2: 8; 1: 1; 8: 2) addition polymers and another polymer) curling conservation rate.The addition polymers that uses is Luviflex Silk TM(BASF), its to have curling conservation rate in VOC 80 batching be 87%.
Table 4: the conservation rate % (1.8wt%w.s. in VOC 80 curls; 25 ℃ and 90% relative humidity)
Polymer only Luviflex?Silk With the ratio of polymer 2: 81: 18: 2
???Luviskol?VA?37?E ????23% ????23 ????75 ????77
???Luviset?CA?66 ????34% ????79 ????67 ????79

Claims (25)

1. the purposes of an addition polymers in pharmaceutical preparation, described addition polymers can obtain by the monomer mixture of the following component of radical polymerization:
(a) ethylenically unsaturated monomer
(b) contain the polyorganosiloxane ramification of polyalkylene oxide.
2. purposes as claimed in claim 1, the use therein polyorganosiloxane ramification (b) that contains polyalkylene oxide are those of following general formula I:
Figure A0081209900021
Wherein: R 2=CH 3Or
Figure A0081209900022
R 3=CH 3Or R 2R 4=H, CH 3,
R 6For can containing the organic group with 1 to 40 carbon atom of amino, carboxylic acid or sulfonate ester group, or, be the anion of mineral acid for C=O,
Radicals R wherein 1Can be identical or different, and,, be aromatic hydrocarbon group for having the cyclic aliphatic hydrocarbon of 3 to 20 carbon atoms derived from aliphatic hydrocarbyl with 1 to 20 carbon atom, or and R 5Identical, wherein:
Figure A0081209900025
Condition is a radicals R 1, R 2Or R 3In at least one be the group that contains polyalkylene oxide defined above,
With n be 1 to 6 integer,
X and y are that to make the molecular weight of polysiloxane block be 300 to 30,000 integer,
A, b can be the integer between 0 to 50, condition be a and b sum greater than 0 and c be 0 or 1.
3. purposes as claimed in claim 1, wherein general formula I has following implication: R wherein 1And R 5Has the implication that claim 2 is given.
4. purposes as claimed in claim 3, wherein general formula I has following implication:
Figure A0081209900032
Wherein
R 1=-CH 3
Figure A0081209900033
R 4=-H ,-COCH 3, C 1-C 4Alkyl
N=1 to 6, particularly 2 to 4
X and y are that to make the molecular weight of polysiloxane block be 1000 to 5000 integer,
A, b can be the integer between 0 to 50, and condition is that a and b sum are greater than 0.
5. as at least one purposes in the claim 1 to 4, wherein
(a) be at least a (methyl) acrylate.
6. as at least one purposes in the claim 1 to 5, wherein
(a) be selected from
(a1) tert-butyl acrylate and
(a2) methacrylic acid.
7. as at least one purposes in the claim 1 to 6, wherein
(a) amount be 50 to 99.9wt% and
(b) amount is 0.1 to 50wt%,
Condition is that these components add and are 100%.
8. as at least one purposes in the claim 1 to 6, wherein
(a1) amount is 49.5 to 99wt%,
(a2) amount is 0.5 to 40wt%,
(b) amount is 0.5 to 20wt%,
Condition is that these components add and are 100%.
9. as at least one the purposes of addition polymers in the claim 1 to 8, as the film former in the pharmaceutical preparation, coating materials and/or binding agent.
10. preparation comprises:
-the addition polymers that can the monomer mixture by the following component of radical polymerization obtains:
(a) ethylenically unsaturated monomer
(b) contain the polyorganosiloxane ramification of polyalkylene oxide
-another polymer is selected from:
Polyvinylpyrrolidone;
The polyethylene caprolactam;
Polyurethane;
Acrylic acid, methyl methacrylate, octyl acrylamide, methacrylic acid fourth
The copolymer of amino ethyl ester and hydroxypropyl methacrylate;
The copolymer of tert-butyl acrylate, ethyl acrylate and methacrylic acid;
The copolymer of ethyl acrylate and methacrylic acid;
N tert butyl acrylamide, ethyl acrylate and acrylic acid copolymer;
The copolymer of vinyl acetate and .beta.-methylacrylic acid and/or neodecanoic acid (vinyl) ester;
The copolymerization of vinyl acetate and/or propionate and N-vinyl pyrrolidone
Thing.
11. a preparation comprises:
-the addition polymers that can the monomer mixture by the following component of radical polymerization obtains:
(a) ethylenically unsaturated monomer
(b) contain the polyorganosiloxane ramification of polyalkylene oxide
-anti-UV light filtrate.
12. as the preparation of claim 10 and/or 11, the use therein polyorganosiloxane ramification (b) that contains polyalkylene oxide is those of following general formula I:
Figure A0081209900051
Wherein: R 2=CH 3Or
Figure A0081209900052
R 3=CH 3Or R 2R 4=H, CH 3,
Figure A0081209900054
R 6For can containing the organic group with 1 to 40 carbon atom of amino, carboxylic acid or sulfonate ester group, or, be the anion of mineral acid for C=O,
Radicals R wherein 1Can be identical or different, and,, be aromatic hydrocarbon group for having the cyclic aliphatic hydrocarbon of 3 to 20 carbon atoms derived from aliphatic hydrocarbyl with 1 to 20 carbon atom, or and R 5Identical, wherein:
Figure A0081209900055
Condition is a radicals R 1, R 2Or R 3In at least one be the group that contains polyalkylene oxide defined above,
With n be 1 to 6 integer,
X and y are that to make the molecular weight of polysiloxane block be 300 to 30,000 integer,
A, b can be the integer between 0 to 50, condition be a and b sum greater than 0 and c be 0 or 1.
13. as the preparation of claim 12, wherein general formula I has following implication:
Figure A0081209900061
R wherein 1And R 5Has the implication that claim 12 is given.
14. as the preparation of claim 13, wherein general formula I has following implication:
Figure A0081209900062
Wherein
R 1=-CH 3
Figure A0081209900063
R 4=-H ,-COCH 3, C 1-C 4Alkyl
N=1 to 6, particularly 2 to 4
X and y are that to make the molecular weight of polysiloxane block be 1000 to 5000 integer,
A, b can be the integer between 0 to 50, and condition is that a and b sum are greater than 0.
15. as at least one preparation in the claim 10 to 14, wherein
(a) be at least a (methyl) acrylate.
16. as at least one preparation in the claim 10 to 15, wherein
(a) be selected from:
(a1) tert-butyl acrylate and
(a2) methacrylic acid.
17. as at least one preparation in the claim 10 to 16, wherein addition polymers can be obtained by 50 to 99.9wt% (a) and 0.1 to 50wt% (b), condition is that these components add and are 100%.
18. as at least one preparation in the claim 10 to 17, wherein addition polymers can by
(a1) (methyl) acrylate of 49.5 to 99wt%,
(a2) another of 0.5 to 40wt% (methyl) acrylate,
(b) polyorganosiloxane ramification of 0.5 to 20wt% following general formula obtains:
Figure A0081209900071
R wherein 1=-CH 3
R 4=-H ,-COCH 3, C 1-C 4Alkyl
N=1 to 6, particularly 2 to 4
X and y are that to make the molecular weight of polysiloxane block be 1000 to 5000 integer,
A, b can be the integer between 0 to 50, condition be a and b sum greater than 0,
Condition is that each component sum is 100%.
19. as at least one the purposes of preparation in pharmaceutical preparation in the claim 10 to 18.
20. as at least one the purposes of preparation in cosmetic formulations in the claim 10 to 18.
21., be used for the fingernail care composition as the purposes of claim 20.
22. the purposes as claim 20 is used for decorative cosmetic preparations.
23. the purposes as claim 22 is used in reference in the nail polish.
24. as at least one preparation in the claim 10 to 18 as the purposes of film former.
25. the purposes of an addition polymers in decorative cosmetic preparations, described addition polymers can obtain by the monomer mixture of the following component of radical polymerization:
(a1) (methyl) acrylate
(a2) another (methyl) acrylate (b) is according to the polyorganosiloxane ramification of following general formula
Figure A0081209900081
R wherein 1=-CH 3
Figure A0081209900082
R 4=-H ,-COCH 3, C 1-C 4Alkyl n=1 to 6, particularly 2 to 4x and y be that to make the molecular weight of polysiloxane block be 1000 to 5000 integer, a, b can be the integer between 0 to 50, condition is that a and b sum are greater than 0.
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