CN1222070A - Aqueous nail coating compsn. containing copolymerized colorants - Google Patents
Aqueous nail coating compsn. containing copolymerized colorants Download PDFInfo
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- CN1222070A CN1222070A CN 96180110 CN96180110A CN1222070A CN 1222070 A CN1222070 A CN 1222070A CN 96180110 CN96180110 CN 96180110 CN 96180110 A CN96180110 A CN 96180110A CN 1222070 A CN1222070 A CN 1222070A
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Abstract
This invention relates to an aqueous nail coating composition and method for coloring nails comprising the use of a water-dispersible, colored sulfopolyester wherein the colorant moiety is incorporated into or onto a carbonyloxy and/or carbonylamide backbone of the sulfopolyester. The sulfopolyesters are uniquely designed to offer cosmetically desirable color coatings on nails.
Description
The list of references of related application
The application requires the rights and interests of No. the 60/009th, 392, provisional application series (1995, December application on the 29th).
Scope of the present invention
The present invention relates to aqueous nail coating composition and comprise use water dispersible, painted sulfonic polyester (wherein the coloring agent group mixes or is attached on the ketonic oxygen base and/or carbonyl acylamino-skeleton of sulfonic polyester) make the fingernail method of colouring.
Background of the present invention
Existing many kinds of nail coating preparations.Most of this nail coating oil are lacquers of nitrocellulose, aryl sulfonic acid amides formaldehyde resin, plasticizer and organic solvent and a small amount of coloring agent and other mixture of ingredients formation.These fingernail lacquers have the decolourising property of poor dampness permeability, fingernail and need long disadvantages such as drying time.In addition, this fingernail lacquer contains volatile organic solvent, can produce the problem of safety, toxicity and environmentology.
Existing film forming generates compositions and is disclosed in United States Patent (USP) the 4th, 939, and 233,4,946,932 and 4,158, in No. 053.United States Patent (USP) the 4th, 939, introduced the film-forming composition that comprises polyester and another kind of polymer No. 233, described polyester has and derives from least a repetitive that at least one is connected in metal sulfamate alkali difunctional. sulfomonomer on the aromatic rings (wherein said functional group is carboxyl or hydroxyl) that comprises, described other polymer has the repetitive that major part derives from vinylacetate, and wherein latter's polymer is generated by polymeric monomer in the water solublity dispersion of described polyester.In nial polish, use this compositions to produce thin film with relatively poor adhesiveness, relatively poor persistency and relatively poor water-fast dissolubility.
United States Patent (USP) the 4th, 946 has been introduced to comprise to have sulfonic group polyester or polyesteramide and comprise for No. 932 and has been derived from one or more α, the film-forming composition of the water solublity dispersion of the polymer of the repetitive of β-unsaturated monomer.In nial polish, use this compositions to produce thin film with relatively poor adhesiveness, relatively poor persistency and relatively poor water-fast dissolubility.
United States Patent (USP) the 4th, 158 has been introduced by two or more for No. 053 and to be selected from alkyl acrylate, the aqueous nail coating preparation that the aqueous emulsion polymerization of methacrylate Arrcostab and distyryl compound makes.On fingernail, use this preparation to produce and have relatively poor adhesiveness and relatively poor persistent slow curing thin film.
United States Patent (USP) the 5th; introduced for 266, No. 322 by the aqueous emulsion (A) of the copolymer that comprises sulfonic polyester and vinyl acetate and dialkyl maleate and comprised the nail coating composition that the aqueous emulsion (B) of acetoacetoxy ethyl methacrylate and vinyl monomer makes.This nail coating composition have good adhesiveness and rate of drying fast.
At the Perfumes of Poucher, Cosmetics, and Soaps (the 9th edition, Chapman﹠amp; Hall N.Y.1993) has introduced the nial polish method of colouring in the 252nd page, and this article claims nial polish generally to use insoluble pigment coloring, because the known pollution skin of water-soluble colorant.Yet the difficult point of using insoluble pigment is that this pigment must be that superfine (＜300 order) is so that remaining in the suspension in storage period for a long time.Required tiny granularity needs by highly energy-consuming, and expensive ball milling or method for grinding obtain.
United States Patent (USP) the 4th, 804 has been introduced the polymeric compositions that comprises ketonic oxygen base and carbonyl acylamino-key No. 719, particularly have combined polymerization or go into the water solublity sulfonic group on the described polymer backbone and the polyester and the polyesteramide ester of coloring agent.Show that these polymer can be used in bonding agent, coating, thin film and the packaging material.Also narrated of the application of the water solublity dispersion of these materials as printing ink, coating and other industrial coating (all having endurance quality).Do not relate to the painted specific field of lasting or non-persistent fingernail.
The case introduction of the various thermally-stabilised industrial coloring agent that are used for producing the coloured polymer by mixing or be added on sulfopolyester polymer is in following United States Patent (USP): 2,571,319; 3,104,233; 3,034,920; 3,372,138; 3,417,048; 3,489,713; 3,278,486; 3,359,230; 3,401,192; 3,417,048; 3,424,708; 4,049,376; 4,080,355; 4,088,650; 4,116,923; 4,141,881; 4,202,814; 4,231,918; 4,267,306; 4,279,802; 4,292,232; 4,344,767; 4,359,570; 4,403,092; 4,477,635; 4,594,400; 4,617,373; 4,617,374; 4,740,581; 4,745,173; 4,808,677; 4,892,922; 4,892,923; 4,958,043; 4,999,418; 5,030,708; 5,032,670; 5,075,491; 5,086,161; 5,102,980; 5,106,942; 5,151,516; 5,179,207; 5,194,571; 5,274,072; 5,281,658, and 5,384,377.Above-mentioned document does not have one piece to point out that the industrial coloring agent of this kind can be used for the human nail.
In a word, the painted sulfonic polyester of water dispersible that uses in the present invention has the chemical constitution of the coloured polymer that is used as nail coating that is different from prior art suggestion use.Water solublity sulfonic group, the combination of chromophoric monomer and can comprise three to four other monomeric sulfonic polyester framing structures are unique.Yet beyond thought is that this kind water dispersible, painted sulfonic polyester can be used for human nail's surface colour valuably.Because the chemical composition between the surface of Concha surface and cellulose base paper product, container and other artificial substrate (ink application and coating are thereon usually) and the significant difference of character, this result is beyond thought.Nobody's prophesy enough moistening adhesiveness and films on latter surface generate and can reappear on the surface of Concha.In addition, from them in industrial purposes (particularly because described application be supposed to be permanent purpose) as printing ink, coating or coating, still can't expect other character as with soap and water by remove on the fingernail, spalling resistance and do not have skin contamination.
General introduction of the present invention
Thereby, an object of the present invention is to provide and use film forming painted sulfonic polyester to make painted compositions of fingernail and method, wherein said thin film adheres to nail surface.
Another object of the present invention provides uses film forming painted sulfonic polyester to make painted compositions of fingernail and method, and wherein said thin film remains on that can to tolerate fingernail under different temperature and the relative humidity condition crooked and do not break and by the pliability that breaks away from the fingernail.
Another purpose of the present invention provides uses film forming painted sulfonic polyester to make painted compositions of fingernail and method, wherein said thin film as when fingernail rubdown, medicated clothing etc., maintain the hardness that enough prevents the color transfer.
An other purpose of the present invention provides uses film forming painted sulfonic polyester to make painted compositions of fingernail and method, and wherein said thin film is metastable, nontoxic and does not stimulate or pollute skin.
These and other purpose of the present invention is by comprising at least a water dispersible sulfonic polyester of using effective dose and reacting the make fingernail method of colouring of coloring agent on fingernail that enters or invest on the described sulfonic polyester skeleton and finish.The described sulfonic polyester that comprises basically with the sour equivalent of mol ratio such as hydroxyl equivalent comprises the reactive group of following reactant and becomes ester derivant: (a) is selected from dicarboxylic acids of aromatic diacid, representative examples of saturated aliphatic diacid, cycloaliphatic diacid and composition thereof; (b) glycol; (c) contain at least one based on the about 25 moles of % of about 4-of the total equivalent of all acid that equals about 200 moles of % and hydroxyl and be connected in sulfonic difunctional. sulfomonomer on aromatic rings or the cycloaliphatic ring, wherein said functional group is selected from hydroxyl, carboxyl and amino; And (d) based on the coloring agent of the total equivalent 1-40 mole % of all acid that equals about 200 moles of % and hydroxyl with formula X-Col-X, wherein Col is that coloring agent residue and X are condensation reaction ketonic oxygen base or the reactive carbonyl acylamino-substituent groups that is selected from hydroxyl, carboxyl, amino, alkyl amino, ester group and acylamino-respectively, and wherein said group has the following formula structure:
Or
R wherein
1Be selected from C
1-C
5Alkyl, C
3-C
8Cycloalkyl and phenyl; And R
2Be hydrogen or R
1
The present invention also relates to comprise the aqueous nail coating composition of two kinds of aqueous emulsions.Aqueous emulsion (A) comprises painted sulfonic polyester and contains the copolymer of vinyl-acetic ester and maleic acid or dialkyl fumarate, the polymerization in the aqueous dispersion of painted sulfonic polyester of wherein said copolymer.Aqueous emulsion (B) comprises the product of acetoacetoxy ethyl alkyl acrylate or acetoacetoxy ethyl alkyl acrylate and vinyl functional monomer reaction.Of the present invention being described in detail
The inventive method is convenient, fast and provide safely and make fingernail painted, preferred staff fingernail and toenail method of colouring, it comprises the painted sulfonic polyester of a kind of water dispersible of using effective dose on fingernail, and wherein the coloring agent reaction enters or invests on the described sulfonic polyester skeleton.Term " effective dose " is meant that naked vision detects painted essential amount as used herein.
Painted sulfonic polyester of the present invention comprises ketonic oxygen base linking group in the about 100 moles of % linearity molecular structures of about 20-and the carbonyl acylamino-linking group of 0-80 mole %.It is about 15000 that the painted sulfonic polyester of the present invention has about 3000-, and the number-average molecular weight of preferred 4000-10000 and the polymer concentration in 25 ℃ of phenol at 60/40 weight portion/sym-tetrachloroethane solution and in the described solvent of 100ml are the logarithmic viscosity number of the 0.1-0.50 that records under the 0.10 gram condition.Described painted sulfonic polyester comprises the sour equivalent (100 moles of %) with mol ratio such as hydroxyl and amino equivalent (100 moles of %) be basic, and the reactive group that comprises diacid, glycol, difunctional. sulfomonomer and coloring agent, and become ester and become the esteramides derivant.
The diacid component of described sulfonic polyester is selected from aromatic diacid (preferably having 8-14 carbon atom), representative examples of saturated aliphatic diacid (preferably having 4-12 carbon atom) and cycloaliphatic diacid (preferably having 8-12 carbon atom).The object lesson of diacid is: terephthalic acids, phthalic acid, isophthalic acid, naphthalene-2,6-diacid, cyclohexane diacid, hexamethylene oxalic acid, biphenyl 4,4 '-diacid, succinic acid, 1,3-propanedicarboxylic acid, adipic acid, Azelaic Acid, decanedioic acid etc.Described sulfonic polyester can be made by above-mentioned two or more diacid.
Should be appreciated that corresponding anhydride, ester and the acyl chlorides of using these acid are included in the term " diacid ".
The diol component of described sulfonic polyester comprises cycloaliphatic glycol (preferably having 6-20 carbon atom) or aliphatic diol (preferably having 3-20 carbon atom).The example of this type of glycol has: ethylene glycol, diethylene glycol, 2,2'-ethylenedioxybis(ethanol)., 1, the 4-cyclohexanedimethanol, 1, ammediol, 1, the 4-butanediol, 1, the 5-pentanediol, 1, the 6-hexanediol, 3-methyl-2, the 4-pentanediol, the 2-methyl isophthalic acid, the 4-pentanediol, 2,2,4-trimethyl-1, the 3-pentanediol, 2-ethyl-1, the 3-hexanediol, 2,2-diethyl-1, ammediol, 1, the 3-hexanediol, 1,4-pair-(hydroxyl-oxethyl) benzene, 2,2-pair-(4-hydroxy-cyclohexyl) propane, 2,4-dihydroxy-1,1,3,3-tetramethyl-ring butane, 2,2-pair-(3-hydroxyl-oxethyl phenyl) propane and 2,2-pair-(4-hydroxyl propoxyl group phenyl) propane.Described sulfonic polyester can be made by two or more above-mentioned glycol.
The diol component of described sulfonic polyester also can comprise having formula: H (OCH
2CH
2)
nPoly-(ethylene glycol) repetitive of OH, wherein n is the integer of about 2-about 500.General poly-(ethylene glycol) mole % that is added with in described scope in n quantity be inversely proportional to.
The difunctional. sulfomonomer component of described sulfonic polyester can be that diacid or its contain sulfonic group (SO
3-) ester, contain sulfonic glycol or contain sulfonic hydroxy acid.The sulfonate cation can be Na
+, Li
+, K
+, NH
4 +With the replacement ammonium.Term " replacement ammonium " is meant the ammonium that replaces with alkyl with 1-4 carbon atom or hydroxy alkyl.Described difunctional. sulfomonomer contains at least one and is connected in sulfonic group on the aromatic rings, and wherein said functional group is hydroxyl, carboxyl or amino.Favourable difunctional. sulfomonomer component be those wherein sulfonate groups be connected in for example component on benzene, naphthalene, xenyl, oxo xenyl, sulfonyl xenyl or the methylene biphenyl basic ring of aromatic acid ring.Preferred sulfomonomer is selected from sulfo group phthalic acid, sulfo group terephthalic acids, sulfoisophthalic acid, 4-sulfo group naphthalene-2,7-diacid and ester thereof.Exist based on the described sulfomonomer of 100 moles of % diacid and 100 moles of % glycol amount with 4-25 mole %.
When described difunctional. sulfomonomer component be 5-sodium for sulfoisophthalic acid or its ester, and described glycol is ethylene glycol or 1, during the mixture of 4-cyclohexanedimethanol and diethylene glycol, obtains preferred result.
But the coloring agent component of described sulfonic polyester contains one or more thermally-stabilised organic compound that has at least one condensation group at first.Term " thermally-stabilised " is meant up to stablizing to being less than about 270 ℃ as used herein.Described coloring agent does not need to grind and is water insoluble after thin film forms.In addition, this coloring agent does not pollute skin.This coloring agent exists with the about 40 moles of % of about 1-based on the amount of total overall reaction thing hydroxyl, carboxyl and amino equivalent.But these equivalents comprise the derivant of its various condensations, comprising: carbalkoxy, aromatic ester base, N-alkyl carbamoyloxy base, acyloxy, chloro carbonyl, carbamoyloxy, N-(alkyl) 2 carbamoyloxies, alkyl amine group, N-phenyl amino formyloxy, hexamethylene acyloxy and carbocyclic ring hexyloxy.
Described coloring agent is expressed from the next:
X-Col-X wherein, Col has the functional group that at least one is selected from hydroxyl, carboxyl and amino equivalent, but and the coloring agent residue of the derivant of condensation, reaching X is condensation reaction carbonyl oxygen base or reactive carbonyl acylamino-substituent group, promptly prepares the group of the monomer reaction of sulfonic polyester with at least one.The example of the denotable reactive group of X comprises hydroxyl, carboxyl, amino, alkyl amino, ester group, acylamino-etc.Described ester group is the arbitrary group with following formula:
Or
Wherein, R
1Be the C that does not replace or replace
1-C
5Alkyl, C
3-C
8The phenyl of cycloalkyl, phenyl or replacement.Preferred R
1Be the about four carbon atom of as many as unsubstituted alkyl for example, methyl and ethyl.R
2Be hydrogen or described R
1Group.The typical case is by R
1And R
2Substituent group on the alkyl of expression comprises: hydroxyl, C
1-C
4Alkoxyl and halogen, phenyl, cyclohexyl, 2-furyl, cyano group and halogen.The typical case is by R
1And R
2Substituent group on the phenyl of expression comprises: C
1-C
4Alkyl, C
1-C
4Alkoxyl and halogen.Reactive group X is preferably hydroxyl, carboxyl, the carbalkoxy or the alkanoyloxy of about 4 carbon atoms of as many as, for example carbomethoxy or acetoxyl group.Be appreciated that X can represent two different reactive groups, for example an X group can be represented hydroxyl, and another X group can be represented carboxyl.
Suitable coloring agent is illustrated in United States Patent (USP) the 4th, 804, and in No. 719, the content of the disclosure is attached among the present invention as a reference at this.Described coloring agent can be made into shades of colour, and usually, wherein any all can be separately or in conjunction with being used to prepare nail coating composition of the present invention.Preferred described coloring agent is selected from following type: methine dyes; Two methine dyeses; Anthraquinone; 3 H-dibenzo [f, ij] isoquinolin-2,7-diketone (Anthrapyridone (anthrapyridones)); Three benzo dioxazines; 5, the two hydrogen quinoxalines of 12-are [2,3-b] azophenlyene (fluorine Yin pyridine (fluorindines)) also; Phthalyl purrocoline pyridine; 2H-1-chromen-2-one (coumarin); 3H-naphtho-[2,1-b] pyran-2-one (benzo coumarin); 4-amino-1,8-naphthalimide; Thioxanthene-9-one; The amino terephthalic acids (or ester) of 2,5 (3)-Fang; Benzo [f] pyrido [1,2-a] indole-6, the 11-diketone; The adjacent benzene diketone (phthalones) of quino; 7H-benzo (de) anthracene-7-ketone (benzanthrone); 7H-benzo [e] pyridine-7-ketone (anthra pyrimidine); 6,15-dihydro-5,9,14,18-anthrzinetetrones (indanthrone); 7H-dibenzo [f, ij] isoquinolin-7-ketone (anthra pyridine); 6H, 18H-pyrido [1,2-a:3,4-b '] two indole-6,13-diketone; Two indole [3,2,1-de:3 ' 2 ' 1 '-ij] [1,5] naphtho-pyridine 6, the 13-diketone; Naphtho-[1 ', 2 ', 3 ': 4,5] quino [2,1-b] quinazoline-5, the 10-diketone; Benzo [f] pyrido [1,2-a] indole-6, the 11-diketone; The 7H-benzimidazole is [2,1-a] [de] isoquinolin-7-ketone also; 5H-benzo [a] phenoxazine-5-ketone; 5H-benzo [a] phenothiazine-5-ketone; Benzo [f] pyrido [1,2-a] indole-6, the 11-diketone; 3,6-diaminourea 1,2,4,5-benzenetetracarboxylic acid imidodicarbonic diamide; Naphthalene [1:4:5:8] tetracarboxylic acid diimide; 3-aryl-2,5-dioxo pyrrolin; Perinones; Perylene; Phthalocyanine; Anthra isothiazole; Quinacridone; The anthra pyrimidone; The phthalyl acridone; Phthalyl phenothiazine and phthalyl phenothiazine-S, the S-dioxide.
Particularly preferred colorant type is methine, two methine, Anthrapyridone, anthraquinone and phthalocyanine.Can mix in the into described painted sulfonic polyester more than a kind of coloring agent.
Described painted sulfonic polyester can be according to United States Patent (USP) the 3rd, 546,008; 3,734,874; 3,779,993; 4,233,196; 4,335, No. 220, particularly United States Patent (USP) the 4th, 804, and the technology that No. 719 described preparations contain the polymer of sulfo group makes, and its disclosed content is attached among the present invention as a reference.
The concentration of described coloring agent in final nail coating composition changes according to the concentration of painted group described in the polymeric colorant and the intrinsic tinctorial strength of painted group.Generally, described painted group can constitute the 1%-40% (weight) of final polymeric colorant.Preferably it is between 10%-30%.
Described painted sulfonic polyester is preferably used with the nail coating composition form that comprises two kinds of aqueous emulsions.Aqueous emulsion (A) comprises sulfonic polyester and contains the copolymer of vinyl acetate and maleic acid dialkyl or fumaric acid dialkyl, the polymerization in the aqueous dispersion of described sulfonic polyester of wherein said copolymer.
Sulfonic polyester in the described aqueous emulsion (A) can be painted sulfonic polyester described herein or uncoloured water dispersible sulfonic polyester.This painted sulfonic polyester also can mix with the uncoloured water dispersible sulfonic polyester of as many as 95% (weight).Suitable uncoloured water dispersible sulfonic polyester comprises the reactive group of diacid described herein, glycol and two sense sulfomonomer, and becomes ester and the derivant that becomes esteramides.Uncoloured water dispersible sulfonic polyester generally can be buied (as Eastman AQ29D, 38D, 38S, 48Ultra,, 55D and 55S) by Eastman Chemical Company.Perhaps, described painted sulfonic polyester can be in aqueous emulsion (A) and (B) mixing back adding.
Described copolymer component (2) has the maleic acid dialkyl of nytril 0-50% (weight) of 50-90% (weight) or the repetitive of fumaric acid dialkyl.Described maleic acid dialkyl or fumaric acid dialkyl have the following formula structure:
Wherein, each R
3Be respectively C
1-C
10Alkyl.The polymerization in the aqueous dispersion that contains sulfonic polyester (1) of described vinyl acetate and maleic acid dialkyl or fumaric acid dialkyl generates copolymer (2).Preferred maleic acid dialkyl is a dibutyl maleate.
Preferred copolymer (2) comprises the unit of the vinyl acetate that derives from about 80% (weight) and derives from the unit of the maleic acid dialkyl of about 20% (weight).Also preferred water emulsion (A) constitutes by the sulfonic polyester (1) of about 5-about 20% (weight) with by the copolymer (2) of about 80-about 95% (weight).Aqueous emulsion (B) contains the acetoacetoxy groups ethyl alkyl acrylate with formula I structure:
Wherein, R
4Be C
1-C
4Alkyl.Preferred acetoacetoxy groups ethyl alkyl acrylate is an acetoacetoxy ethyl methacrylate.Aqueous emulsion (B) also can contain monomeric product of vinyl functional group of II, III and IV under acetoacetoxy ethyl alkyl acrylate and the formula and composition thereof: CH
2=CH-COOR
5(II)
Wherein, R
5Be to be selected from the C that does not replace or replace
1-C
10Alkyl, C
3-C
8The phenyl of cycloalkyl, phenyl and replacement; R
6Be hydrogen or methyl; R
7Be C
1-C
10Alkyl or C
1-C
10Alkylidene-N (R
9) R
10, R wherein
9And R
10Be selected from hydrogen, C respectively
1-C
2Alkyl and hydroxyl C
1-C
4Alkyl; And R
8Be hydrogen or C
1-C
6Alkyl.
Term " phenyl of replacement " is meant with one or more C of being selected from
1-C
4Alkyl, C
1-C
4The phenyl that the group of alkoxyl and halogen replaces.The example of the phenyl that replaces has: 4-aminomethyl phenyl, 3,4-3,5-dimethylphenyl, the 3-aminomethyl phenyl, 2-chlorophenyl, 4-chlorophenyl, 2,5-dichloro-phenyl, 4-ethoxyl phenenyl, 4-just-butyl phenyl, the 3-isopropyl phenyl, uncle 4--butoxy phenyl, 2-ethyoxyl-5-aminomethyl phenyl and 2,5-diethoxy phenyl.
The monomeric mixture of this kind vinyl functional also can be with the reaction of acetoacetoxy ethyl methacrylate and as aqueous emulsion (B).Aqueous emulsion (B) is with based on whole aqueous emulsions (A) and (B) 15-70% of gross weight (weight), and the amount of preferred 15-25% (weight) exists.
The example of suitable formula II acrylate is: acrylic acid methyl ester., ethyl acrylate, butyl acrylate, benzyl acrylate, acrylic acid bran ester, tetrahydrofurfuryl acrylate, acrylic acid methoxy ethyl ester, acrylic acid ethoxy ethyl ester, 2-EHA, acrylic acid ring pentyl ester, cyclohexyl acrylate, acrylic acid 2,3-epoxy radicals-1-propyl ester, acrylic acid 2-dimethylaminoethyl and dodecyl acrylate.
The example of suitable formula III methacrylate is: methylmethacrylate, ethyl methacrylate, methacrylate propyl ester, butyl isocrotonate, methacrylate phenyl ester, isobutene. acid benzyl ester, propylene glycol list methacrylate, methacrylate octadecane ester, methacrylate tetrahydrochysene bran ester, methacrylate bran ester, methacrylate 2-lignocaine ethyl ester and methacrylate hydroxyl ethyl ester.
Suitable formula IV aromatic ethylene base functional monomer's example is styrene, 4-vinyltoluene, 2-vinyltoluene, a-methyl styrene, 4-cumene ethylene and di isopropenylbenzene.
Except that above-mentioned formula II, III and IV three class ethylene functional monomers, can be with other optional vinyl functional monomer and the reaction of acetoacetoxy groups ethyl alkyl acrylate, yet, arbitrary optional ethylene functional monomer's total amount can not surpass formula II,, III and IV monomeric 10% (weight) of vinyl functional, and preferably be less than 5% (weight).The monomeric specific nature of optional vinyl functional is unimportant, as long as the monomeric amount of arbitrary optional vinyl functional has no adverse effect to the film property of described compositions.
Have been found that use thin film of the present invention generate the adhesiveness of nail coating composition of compositions and durability can be by in the present composition, mixing fixative and cross-linking agent improves.This fixative or cross-linking agent preferably directly were applied to fingernail before using described nail coating composition.Perhaps, this fixative or cross-linking agent can mix in the described nail coating composition before the described nail coating composition of application is on fingernail.In water-soluble, the acetone of concentration that this fixative or cross-linking agent can about 1-about 10% (weight) or the mixture of water and acetone.Preferred solution contains 1% (weight) ZnCl that has an appointment
2, 4% (weight) water and 95% (weight) acetone, or contain the acetone of 90-95% (weight) and the solution of 5-10% (weight) triamine.
Useful fixative or cross-linking agent comprise divalent metal, trivalent metal, aldehyde, aminoacid, diamidogen and triamine.Concrete example comprises: zinc chloride, zinc acetate, formaldehyde, alanine and cystine.Preferred amine comprises by gathering (oxyalkylene) for example polymeric part of JEFFAMINE 600 and 2000 (deriving from Texaco Chemical Company) formation.Had been found that before described nail coating composition is applied to fingernail fixative is mixed under the situation in the nail coating composition that contains compositions of the present invention, formaldehyde is effective especially as fixative.
Many other compositions can add in the nail coating composition of the present invention, to strengthen the operating characteristic of this nail coating.For example, preservative agent, dispersant, wetting agent, coalescent, defoamer, buffer agent, chelating agen, UV absorbers, stabilizing agent, filler, thickening agent such as bentonite, opacifier such as titanium dioxide, guanine, bismuth oxychloride and pearlescent pigment etc. can be included in wherein with the amount based on the as many as of whole compositionss about 5.0% (weight) usually.These additives and to be applied in the present technique field be known.Only otherwise influencing the present invention finishes its purpose, can use arbitrary described chemical compound.
Aqueous emulsion (A) and (B) with the aqueous emulsion polymer manufacture.Under the situation of aqueous emulsion (A), described vinyl acetate and maleic acid dialkyl are added in the aqueous dispersion of sulfonic polyester and cause the method polymerization of radical polymerization routinely in emulsion or the suspension polymerization.This polymerization can cause by water solublity radical initiator well-known in the art such as sodium peroxydisulfate or oil-soluble initiator such as benzoyl peroxide.Other useful initiator comprises: non-reduced oxidation initiator, as: persulfate, hydrogen peroxide and organic peroxide; The reduction-oxidation initiator, as: sodium peroxydisulfate, sodium sulfite, sodium metabisulfite, sodium dithionite, sodium thiosulfate and sodium formaldehyde sulphoxylate.The reduction-oxidation initiator needs activator, as: ferrous sulfate heptahydrate and ammonium ferric sulfate.Preferred initiator is persulfate, sodium formaldehyde sulphoxylate and ferrous sulfate heptahydrate.
Be used for the painted sulfonic polyester of the present invention very thickness that generally greater than 30% solid concentration the time, becomes.Thereby described reaction is generally with holosteric about 30% or be less than 30% sulfonic polyester dispersion and begin.Yet described water dispersible sulfonic polyester dispersion by the inventive method preparation can finally make with the concentration as many as of total solid about 65%.The increase of described solid concentration is finished by the amount (if any, adding with vinyl acetate and maleic acid dialkyl) of control water in polymerization process.By reducing the amount that adds entry in the polymerization process, the content as many as about 65% that increases total solid is possible.
In preferred embodiments, described painted sulfonic polyester made by molten gathering, and contained the 5-35% that has an appointment (weight), and the aqueous dispersion of the total solid of preferred 10%-30% is directly to be made by described sulfonic polyester.Then the mixture of vinyl acetate, maleic acid dialkyl and polymerization initiator is added in the aqueous dispersion of sulfonic polyester and initiated polymerization produces aqueous dispersion.The aqueous dispersion that makes like this can be that the content of about 10%-about 65% prepares with total solids content.
Under the situation of aqueous emulsion (B), mix with water, initiator and surfactant separately or with formula II, III or the blended acetoacetoxy groups ethyl propylene of IV vinyl functional monomer acid esters, and by the free radical polymerization in the method for conventional emulsions or suspension polymerization.This polymerization can cause by water solublity radical initiator well-known in the art such as sodium peroxydisulfate or oil-soluble initiator such as benzoyl peroxide.Other useful initiator comprises: non-reduced oxidation initiator, as: persulfate, hydrogen peroxide, and organic peroxide; Redox initiator, as: sodium peroxydisulfate, sodium sulfite, sodium metabisulfite, sodium dithionite, sodium thiosulfate and sodium formaldehyde sulfoxylate.The reduction-oxidation initiator needs activator, as: ferrous sulfate heptahydrate and ammonium ferric sulfate.Preferred initiator is a persulfate, sodium formaldehyde sulfoxylate and ferrous sulfate heptahydrate.
Can use more than-kind surfactant comprise the component of anion and non-anion surfactant.Cationic surfactant seldom uses.Preferred anionic and non-anion surfactant.The example of suitable non-ionic surface active agent is: the alkyl resin of alcohol-ethylene oxide condensate, fatty acid-ethylene oxide condensate, phenol-ethylene oxide condensate, modification and sorbitol-fatty acid addition product.
Preferred nonionic is the alkyl resin of phenol-ethylene oxide condensate and modification.Suitable examples of anionic surfactants is polyether sulphur acid esters, dialkyl sulfosuccinate succinate, alkyl and alkyl aryl sulfonate, dialkyl sulfosuccinate succinamide, alkyl sulfate and phosphate ester.The preferred anionic surfactants surfactant is polyether sulphur acid esters and alkyl sulfonic ester.
In order to obtain the most effective utilization of nail coating composition of the present invention, be recommended in application nail coating composition of the present invention and clean fingernail before.Useful clean cpd comprises ethyl acetate, acetone, toluene, dimethylbenzene etc.
Following indefiniteness embodiment further specifies the preparation of enforcement of the present invention: embodiment 1 red polymeric colorant.
1 of the diethylene glycol of the dimethyl isophthalate of preparation 51.6g (0.27mol), the dimethyl sulfo group isophthalic acid sodium of 24.9g (0.84mol), 58.3g (0.55mol), 11.4g (0.79mol), 1 of the sodium acetate of 4-cyclohexanedimethanol, 0.75g (0.009mol) and 10g (0.024mol), the mixture of two (3-hydroxyl-2, the 2-dimethyl propyl amino) anthraquinones of 5-.This mixture is placed flask at the bottom of the garden, and add q.s just-the butanols titanium that contains the 0.03g/ml titanium in the butanol solution obtains its mixture of 75ppm titanium concentration.It is in 200 ℃ the heating bath that this flask is immersed temperature.Temperature is risen to 220 ℃ and keep and be warming up to 250 ℃ and kept one hour in one hour then.Evacuation 15 minutes bleeds off vacuum then and removes heating bath and obtains the solid polymerization coloring agent, and grinds and analyze.
The analysis of this polymeric colorant shows number-average molecular weight (M
N) be 4662 and Tg be 51.54 ℃.Nuclear magnetic resonance, NMR shows that this polymeric colorant contains the dye molecule of 9.1% (weight).The preparation of embodiment 2 aqueous nail coating compositions.
Red polymeric colorant 10g with embodiment 1 preparation, under high shear mixing, add among the AQUAREZ 7 that 90g contains acrylate/acetoacetoxy groups ethyl methacrylate ester copolymer and sulfonic polyester (deriving from Eastman Chemical Company), and be heated to 55 ℃.Gained red nail oil is applied to fingernail.This nial polish is provided in level and smooth, the glossy coating on the fingernail.The preparation of embodiment 3 aqueous nail coating compositions
With the red polymeric colorant 15g of embodiment 1 preparation, under high shear mixing, add among the 85g AQUAREZ7 and be heated to 55 ℃.Gained red nail oil is applied to fingernail.This nial polish is more more viscous than the nial polish that embodiment 2 makes, and is provided in level and smooth, the glossy coating on the fingernail.The preparation of embodiment 4 red polymeric colorant
1 of the diethylene glycol of the dimethyl isophthalate of preparation 79.51g (0.41mol), the dimethyl sulfo group isophthalic acid sodium of 26.64g (0.09mol), 54.0g (0.51mol), 37.44g (0.25mol), 1 of the sodium acetate of 4-cyclohexanedimethanol, 0.75g (0.009mol) and 15g (0.036mol), the mixture of two (3-hydroxyl-2, the 2-dimethyl propylene amino) anthraquinones of 5-.This mixture is placed flask at the bottom of the garden, and add q.s just-the butanols titanium that contains the 0.03g/ml titanium in the butanol solution, obtain its mixture of 75ppm titanium concentration.It is in 200 ℃ the heating bath that this flask is immersed temperature.Temperature is risen to 220 ℃ and kept one hour, be warming up to 250 ℃ and kept one hour then.Evacuation 15 minutes bleeds off vacuum then and removes heating bath and obtains the solid polymerization coloring agent, and grinds and analyze.
The analysis of this polymeric colorant shows number-average molecular weight (M
N) be 6878 and Tg be 60.05 ℃.Nuclear magnetic resonance, NMR shows that this polymeric colorant contains the dye molecule of 9.25% (weight).The preparation of embodiment 5 aqueous nail coating compositions
With the red polymeric colorant 10g of embodiment 4 preparation, under high shear mixing, add among the 90g AQUAREZ 7 and be heated to 55 ℃.Gained red nail oil is applied to fingernail.This nial polish is more more viscous than the nial polish that embodiment 2 or 3 makes, and this nial polish is provided in level and smooth, the glossy coating on the fingernail.The preparation of embodiment 6 red polymeric colorant dispersions.
1 of the diethylene glycol of the dimethyl isophthalate of preparation 63.27g (0.33mol), the dimethyl sulfo group isophthalic acid sodium of 19.18g (0.065mol), 28.52g (0.27mol), 26.36g (0.18mol), 1 of the sodium acetate of 4-cyclohexanedimethanol, 0.75g (0.009mol) and 35g (0.085mol), the mixture of two (3-hydroxyl-2, the 2-dimethyl propylene amino) anthraquinones of 5-.This mixture is placed flask at the bottom of the garden, and add q.s just-the butanols titanium that contains the 0.03g/ml titanium in the butanol solution, obtain its mixture of 75ppm titanium concentration.It is in 200 ℃ the heating bath that this flask is immersed temperature.Temperature is risen to 220 ℃ and kept one hour, be warming up to 250 ℃ and kept one hour then.Evacuation 15 minutes bleeds off vacuum then and removes heating bath and obtains the solid polymerization coloring agent, and grinds and analyze.
The analysis of this polymeric colorant shows number-average molecular weight (M
N) be 5987 and Tg be 74.46 ℃.Nuclear magnetic resonance spectroscopy shows that this polymeric colorant contains the dye molecule of 25.3% (weight).
This polymeric colorant 110g is dispersed to the red polymeric colorant dispersion that obtains containing 28% polymeric colorant in the boiling deionized water of 275ml.The preparation of embodiment 7 aqueous nail coating compositions.
Preparation contains the mixture of the deionized water of 76% the red polymeric colorant dispersion that makes according to embodiment 6 and 24%.This mixture is applied to fingernail.This mixture is topped on fingernail and form thin film.This thin film is removed from fingernail with soap and scrub water.The preparation of embodiment 8 aqueous nail coating compositions
By mixing red polymeric colorant dispersion that 95% embodiment 6 makes and 5% Eastman AQ 55s (the sulfonated polyester of non-staining) preparation mixture in 80 ℃.This non-staining sulfonic polyester is easy to infiltrate in the colorant dispersion.This mixture is applied to fingernail.
This embodiment shows that the commodity sulfonic polyester of colourless, the aqueous dispersion of being buied by Eastman Chemical Company such as Eastman AQ 29D, 38D, 38S, 48D, 48S, 55D and 55S and nail coating composition of the present invention are compatible.
Nail coating composition of the present invention provides the thin film of strong adhesion in nail surface.In addition, this thin film can keep pliability under different temperature and the relative humidity condition so that the tolerance fingernail is crooked and do not break and by fingernail on break away from.In addition, this thin film is at the fingernail rubdown, keeps the hardness that prevents that enough color from shifting during medicated clothing etc.This thin film is a safety, nontoxic and do not stimulate or pollute skin.
Although the present invention specifically introduces with reference to some specific embodiment, yet should be understood that the person skilled in the art in present technique field can change and changes it.The present invention only is subject to the content of following claim.
Claims (29)
1. comprise that coloring agent that at least a water dispersible sulfonic polyester of using effective dose and a kind of reaction entered or invested described sulfonic polyester skeleton makes the fingernail method of colouring on fingernail.
2. the process of claim 1 wherein and comprise the reactive group of following reactant and become ester derivant described comprising basically with the painted sulfonic polyester of the sour equivalent of mol ratios such as hydroxyl equivalent:
(a) be selected from the diacid of aromatic diacid, representative examples of saturated aliphatic diacid, cycloaliphatic diacid and composition thereof;
(b) glycol;
(c) based on the sulfonic difunctional. sulfomonomer that at least one is connected in aromatic rings or cycloaliphatic ring that contains of the about 25 moles of % of about 4-of total equivalent of all acid that equals about 200 moles of % and hydroxyl, wherein said functional group is selected from hydroxyl, carboxyl and amino; And
(d) based on the coloring agent of the 1-40 mole % of the total equivalent that equals about 200 moles of % all acids and hydroxyl with formula X-Col-X, wherein Col is the coloring agent residue, but reaching X is the condensation that is selected from hydroxyl, carboxyl, amino, alkyl amino, ester group and acylamino-respectively, reactive ketonic oxygen base or reactive carbonyl acylamino-substituent group, and wherein said group has the following formula structure:
Or
R wherein
1Be selected from C
1-C
5Alkyl, C
3-C
8Cycloalkyl and phenyl; And R
2Be hydrogen or R
1
3. the method for claim 2, the X of wherein said coloring agent is selected from hydroxyl, carboxyl, has the carbalkoxy and the acyloxy of 4 carbon atoms of as many as.
4. the method for claim 3, wherein X is selected from carbomethoxy and acetoxyl group.
5. the method for claim 2, wherein said coloring agent is selected from: methine dyes, two methine dyeses, anthraquinone, 3H-dibenzo [f, ij] isoquinolin-2,7-diketone (Anthrapyridone (anthrapyridones)), three benzo dioxazines, 5, the two hydrogen quinoxalines of 12-also [2,3-b] azophenlyene (fluorine Yin pyridine (fluorindines)), phthalyl purrocoline pyridine, 2H-1 chromen-2-one (coumarin), 3H-naphtho-[2,1-b] pyran-2-one (benzo coumarin), 4-amino-1, the 8-naphthalimide, thioxanthene-9-one, 2, the amino terephthalic acids (or ester) of 5 (3)-Fang, benzo [f] pyrido [1,2-a] indole-6, the 11-diketone, the adjacent benzene diketone (phthalones) of quino, 7H-benzo (de) anthracene-7-ketone (benzanthrone), 7H-benzo [e] pyridine-7-ketone (anthra pyrimidine), 6,15-dihydro-5,9,14,18-anthrzinetetrones (indanthrone), 7H-dibenzo [f, ij] isoquinolin-7-ketone (anthra pyridine), 6H, 18H-pyrido [1,2-a:3,4-b '] two indole-6, the 13-diketone, two indole [3,2,1-de:3 ' 2 ' 1 '-ij] [1,5] the naphtho-pyridine 6, the 13-diketone, naphtho-[1 ', 2 ', 3 ': 4,5] quino [2,1-b] quinazoline-5, the 10-diketone, benzo [f] pyrido [1,2-a] indole-6, the 11-diketone, 7H-benzimidazole also [2,1-a] [de] isoquinolin-7-ketone, 5H-benzo [a] phenoxazine-5-ketone, 5H-benzo [a] phenothiazine-5-ketone, benzo [f] pyrido [1,2-a] indole-6, the 11-diketone, 3,6-diaminourea 1,2,4,5-benzenetetracarboxylic acid imidodicarbonic diamide, naphthalene [1:4:5:8] tetracarboxylic acid diimide, 3-aryl-2,5-dioxo pyrrolin, perinones perylene, phthalocyanine, anthra isothiazole, quinacridone, the anthra pyrimidone, the phthalyl acridone, phthalyl phenothiazine and phthalyl phenothiazine-S, S-dioxide and composition thereof.
6. the method for claim 5, wherein said coloring agent is selected from: methine dyes, two methine dyes, Anthrapyridone, anthraquinone and phthalocyanine.
7. the method for claim 2, the logarithmic viscosity number of wherein said sulfonic polyester is the about 0.50dL/g of about 0.10-.
8. the method for claim 7, wherein said sulfonic polyester has the number-average molecular weight of about 3000-about 15000.
9. comprise the aqueous nail coating composition that water dispersible sulfonic polyester and reaction entered or invested the coloring agent of described sulfonic polyester skeleton.
10. aqueous nail coating composition comprises:
(A) water dispersible, painted sulfonic polyester, the carbon back oxygen base and/or the carbonyl amide backbone of painted sulfonic polyester mixed into or invested to wherein said coloring agent group; With
(B) aqueous emulsion comprises:
(1) non-staining, water dispersible sulfonic polyester;
(2) the nytril 0-50% (weight) with 50-90% (weight) has the copolymer of the repetitive of the maleic acid dialkyl of following formula structure or fumaric acid dialkyl:
Wherein, R
3Independently be C
1-C
10Alkyl; With
(3) have the acetoacetoxy groups ethyl alkyl acrylate of following formula:
Wherein, R
4Be C
1-C
4Alkyl, its condition are that described aqueous nail coating composition has total solids content for about 65% (weight) of about 30-.
11. the aqueous nail coating composition comprises:
(A) aqueous emulsion of 30-85% (weight) comprises:
(1) comprise basically painted sulfonic polyester with the sour equivalent of mol ratio such as hydroxyl equivalent, comprise the reactive group of following reactant and become ester derivant:
(a) be selected from the diacid of aromatic diacid, representative examples of saturated aliphatic diacid, cycloaliphatic diacid and composition thereof;
(b) glycol;
(c) based on the sulfonic difunctional. sulfomonomer that at least one is connected in aromatic rings or cycloaliphatic ring that contains of the about 25 moles of % of about 4-of total equivalent of all acid that equals about 200 moles of % and hydroxyl, wherein said functional group is selected from hydroxyl, carboxyl and amino; And
(d) based on the coloring agent of the 1-40 mole % of the total equivalent that equals about 200 moles of % all acids and hydroxyl with formula X-Col-X, wherein Col is the coloring agent residue, but reaching X is the condensation that is selected from hydroxyl, carboxyl, amino, alkyl amino, ester group and acylamino-respectively, reactive ketonic oxygen base or reactive carbonyl acylamino-substituent group, and wherein said group has the following formula structure:
Or
R wherein
1Be selected from C
1-C
5Alkyl, C
3-C
8Cycloalkyl and phenyl; And R
2Be hydrogen or R
1And
(2) the nytril 0-50% (weight) with 50-90% (weight) has the copolymer of the repetitive of the maleic acid dialkyl of following formula structure or fumaric acid dialkyl:
The polymerization in the aqueous dispersion of sulfonic polyester of this copolymer, wherein, R
3Independent is C
1-C
10Alkyl; With
(B) aqueous emulsion of 15-70% (weight) comprises: the acetoacetoxy groups ethyl alkyl acrylate with following formula:
Or acetoacetoxy groups ethyl alkyl acrylate be selected from the monomeric product of following vinyl functional: CH
2=CH-COOR
5 
And composition thereof; Wherein, R
4Be C
1-C
4Alkyl; R
5Be selected from C
1-C
10Alkyl, C
3-C
8Cycloalkyl and phenyl; R
6Be hydrogen or methyl; R
7Be C
1-C
10Alkyl or C
1-C
10Alkylidene-N (R
9) R
10, R wherein
9And R
10Be selected from hydrogen, C respectively
1-C
2Alkyl and hydroxyl C
1-C
4Alkyl; And R
8Be hydrogen or C
1-C
6Alkyl, condition are that total solids content is 30-65% (weight) in the described nail coating composition.
12. the aqueous nail coating composition of claim 10 wherein, contains fixative in addition.
13. the aqueous nail coating composition of claim 12, wherein said fixative is selected from divalent metal, trivalent metal, aldehyde, aminoacid, diamidogen and triamine.
14. the aqueous nail coating composition of claim 11, wherein said diacid are selected from terephthalic acids, phthalic acid, isophthalic acid, naphthalene-2,6-diacid, cyclohexane diacid, hexamethylene oxalic acid and composition thereof.
15. the aqueous nail coating composition of claim 14, wherein said diacid is an isophthalic acid.
16. the aqueous nail coating composition of claim 11, wherein said glycol are selected from ethylene glycol, diethylene glycol, 2,2'-ethylenedioxybis(ethanol)., 1,4-cyclohexanedimethanol and composition thereof.
17. the aqueous nail coating composition of claim 16, wherein said glycol are diethylene glycol and 1, the 4-cyclohexanedimethanol.
18. the aqueous nail coating composition of claim 17, wherein said two sense sulfomonomer are selected from sulfo group phthalic acid, sulfo group terephthalic acids, sulfoisophthalic acid, 4-sulfo group naphthalene-2,7-diacid and ester thereof.
19. the aqueous nail coating composition of claim 18, wherein said two sense sulfomonomer are that 5-sodium is for sulfoisophthalic acid.
20. the aqueous nail coating composition of claim 11, wherein said acetoacetoxy groups ethyl alkyl acrylate is an acetoacetoxy groups ethyl methacrylate.
21. the aqueous nail coating composition of claim 11, wherein said vinyl functional monomer are selected from acrylate, methacrylate, aromatic ethylene base functional monomer and composition thereof.
22. the aqueous nail coating composition of claim 21, wherein said vinyl functional monomer is to be selected from following acrylate: acrylic acid methyl ester., ethyl acrylate, butyl acrylate, benzyl acrylate, acrylic acid bran ester, tetrahydrofurfuryl acrylate, acrylic acid methoxyl group ethyl ester, acrylic acid ethoxy ethyl ester, 2-EHA, acrylic acid ring pentyl ester, cyclohexyl acrylate, acrylic acid 2,3-epoxy radicals-1-propyl ester, acrylic acid 2-dimethylaminoethyl, dodecyl acrylate and composition thereof.
23. the aqueous nail coating composition of claim 21, wherein said vinyl functional monomer is to be selected from following methacrylate: methylmethacrylate, ethyl methacrylate, methacrylate propyl ester, butyl isocrotonate, methacrylate phenyl ester, isobutene. acid benzyl ester, propylene glycol list methacrylate, methacrylate octadecane ester, methacrylate tetrahydrochysene bran ester, methacrylate bran ester, methacrylate 2-lignocaine ethyl ester, methacrylate hydroxyl ethyl ester and composition thereof.
24. the aqueous nail coating composition of claim 23, wherein said vinyl functional monomer is selected from butyl acrylate, methylmethacrylate, ethyl acrylate and composition thereof.
25. the aqueous nail coating composition of claim 21, wherein said vinyl functional monomer are to be selected from following aromatic ethylene base functional monomer: styrene, 4-vinyltoluene, 2-vinyltoluene, a-methyl styrene, 4-cumene ethylene, di isopropenylbenzene and composition thereof.
26. prepare the method for aqueous nail coating composition, comprising:
(I) preparation comprises basically the painted sulfonic polyester with the sour equivalent of mol ratio such as hydroxyl equivalent, comprises the reactive group of following reactant and becomes ester derivant:
(a) be selected from the diacid of aromatic diacid, representative examples of saturated aliphatic diacid, cycloaliphatic diacid and composition thereof;
(b) glycol;
(c) based on the sulfonic difunctional. sulfomonomer that at least one is connected in aromatic rings or cycloaliphatic ring that contains of the about 25 moles of % of about 4-of total equivalent of all acid that equals about 200 moles of % and hydroxyl, wherein said functional group is selected from hydroxyl, carboxyl and amino; And
(d) based on the coloring agent of the 1-40 mole % of the total equivalent that equals about 200 moles of % all acids and hydroxyl with formula X-Col-X, wherein Col is the coloring agent residue, but reaching X is the condensation that is selected from hydroxyl, carboxyl, amino, alkyl amino, ester group and acylamino-respectively, reactive ketonic oxygen base or reactive carbonyl acylamino-substituent group, and wherein said group has the following formula structure:
Or
R wherein
1Be selected from C
1-C
5Alkyl, C
3-C
8Cycloalkyl and phenyl; And R
2Be hydrogen or R
1And
(II) generates the aqueous emulsion (A) be included in the described sulfonic polyester of preparation in the step (I), and the nytril 0-50% (weight) that polymerization has a 50-90% (weight) in the aqueous dispersion of described sulfonic polyester has the copolymer of the repetitive of the maleic acid dialkyl of following formula structure or fumaric acid dialkyl:
Wherein, R
3Independent is C
1-C
10Alkyl; And respectively
(III) preparation contains the aqueous emulsion (B) of following ingredients: the acetoacetoxy groups ethyl alkyl acrylate of tool following formula:
Or acetoacetoxy groups ethyl alkyl acrylate and the product that is selected from following vinyl functional monomer reaction: CH
2=CH-COOR
5 
And composition thereof; Wherein, R
4Be C
1-C
4Alkyl; R
5Be selected from C
1-C
10Alkyl, C
3-C
8Cycloalkyl and phenyl; R
6Be hydrogen or methyl; R
7Be C
1-C
10Alkyl or C
1-C
10Alkylidene-N (R
9) R
10, R wherein
9And R
10Be selected from hydrogen, C respectively
1-C
2Alkyl and hydroxyl C
1-C
4Alkyl; And R
8Be hydrogen or C
1-C
6Alkyl; With
(IV) mixing water emulsion (A) reaches (B), thereby obtains having the aqueous nail coating composition of total solids content for about 65% (weight) of about 30-.
27. the method for claim 26 wherein in mixing water emulsion (A) and step (B) (IV) before, adds fixative in the aqueous emulsion (B).
28. prepare the method for aqueous nail coating composition, comprising:
(I) preparation comprises basically the sulfonic polyester with the sour equivalent of mol ratio such as hydroxyl equivalent, and this sulfonic polyester comprises the reactive group of following reactant and becomes ester derivant:
(a) be selected from the diacid of aromatic diacid, representative examples of saturated aliphatic diacid, cycloaliphatic diacid and composition thereof;
(b) glycol; With
(c) based on the sulfonic difunctional. sulfomonomer that at least one is connected in aromatic rings or cycloaliphatic ring that contains of the about 25 moles of % of about 4-of total equivalent of all acid that equals about 200 moles of % and hydroxyl, wherein said functional group is selected from hydroxyl, carboxyl and amino;
(II) generates the aqueous emulsion (A) be included in the described sulfonic polyester of preparation in the step (I), and the nytril 0-50% (weight) that polymerization has a 50-90% (weight) in the aqueous dispersion of described sulfonic polyester has the copolymer of the repetitive of the maleic acid dialkyl of following formula structure or fumaric acid dialkyl:
Wherein, R
3Independent is C
1-C
10Alkyl; And respectively
(III) preparation contains the aqueous emulsion B of following ingredients: the acetoacetoxy groups ethyl alkyl acrylate of tool following formula:
Or acetoacetoxy groups ethyl alkyl acrylate and the product that is selected from following vinyl functional monomer reaction: CH
2=CH-COOR
5 
And composition thereof; Wherein, R
4Be C
1-C
4Alkyl; R
5Be selected from C
1-C
10Alkyl, C
3-C
8Cycloalkyl and phenyl; R
6Be hydrogen or methyl; R
7Be C
1-C
10Alkyl or C
1-C
10Alkylidene-N (R
9) R
10, R wherein
9And R
10Be selected from hydrogen, C respectively
1-C
2Alkyl and hydroxyl C
1-C
4Alkyl; And R
8Be hydrogen or C
1-C
6Alkyl;
(IV) mixing water emulsion (A) reaches (B), forms the emulsion mixture; With
(V) adds the painted sulfonic polyester that comprises basically with the sour equivalent of mol ratio such as hydroxyl equivalent in the emulsion mixture that step (IV) forms, thereby obtain the aqueous nail coating composition of total solids content for about 65% (weight) of about 30-, described painted sulfonic polyester comprises the reactive group of following reactant and becomes ester derivant:
(a) be selected from the diacid of aromatic diacid, representative examples of saturated aliphatic diacid, cycloaliphatic diacid and composition thereof;
(b) glycol;
(c) based on the sulfonic difunctional. sulfomonomer that at least one is connected in aromatic rings or cycloaliphatic ring that contains of the about 25 moles of % of about 4-of total equivalent of all acid that equals about 200 moles of % and hydroxyl, wherein said functional group is selected from hydroxyl, carboxyl and amino; And
(d) based on the coloring agent of the 1-40 mole % of the total equivalent that equals about 200 moles of % all acids and hydroxyl with formula X-Col-X, wherein Col is the coloring agent residue, but reaching X is the condensation that is selected from hydroxyl, carboxyl, amino, alkyl amino, ester group and acylamino-respectively, reactive ketonic oxygen base or reactive carbonyl acylamino-substituent group, and wherein said group has the following formula structure:
Or
R wherein
1Be selected from C
1-C
5Alkyl, C
3-C
8Cycloalkyl and phenyl; And R
2Be hydrogen or R
1
29. prepare the method for aqueous nail coating composition, comprise mixing:
(A) water dispersible, painted sulfonic polyester is wherein mixed described coloring agent group into or invests the ketonic oxygen base and/or the carbonyl amide backbone of painted sulfonic polyester; With
(B) aqueous emulsion comprises:
(1) but the dispersible sulfonic polyester of non-staining water;
(2) the nytril 0-50% (weight) with 50-90% (weight) has the copolymer of the repetitive of the maleic acid dialkyl of following formula structure or fumaric acid dialkyl:
Wherein, R
3Independently be C
1-C
10Alkyl; With
(3) have the acetoacetoxy groups ethyl alkyl acrylate of following formula:
Wherein, R
4Be C
1-C
4Alkyl is to obtain the having aqueous nail coating composition that total solids content is about 65% (weight) of about 30-.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 96180110 CN1222070A (en) | 1995-12-29 | 1996-12-17 | Aqueous nail coating compsn. containing copolymerized colorants |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US60/009,392 | 1995-12-29 | ||
| US08/728,457 | 1996-10-10 | ||
| CN 96180110 CN1222070A (en) | 1995-12-29 | 1996-12-17 | Aqueous nail coating compsn. containing copolymerized colorants |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1222070A true CN1222070A (en) | 1999-07-07 |
Family
ID=5127748
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 96180110 Pending CN1222070A (en) | 1995-12-29 | 1996-12-17 | Aqueous nail coating compsn. containing copolymerized colorants |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1222070A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104546544A (en) * | 2013-10-09 | 2015-04-29 | 施乐公司 | Nail polish compositions |
-
1996
- 1996-12-17 CN CN 96180110 patent/CN1222070A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104546544A (en) * | 2013-10-09 | 2015-04-29 | 施乐公司 | Nail polish compositions |
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