Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Mixing of two or more solid polymers; mixing of solid...
Reexamination Certificate
1999-11-16
2001-12-11
Seidleck, James J. (Department: 1711)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
Mixing of two or more solid polymers; mixing of solid...
C526S264000, C424S070100, C424S070110, C424S070160
Reexamination Certificate
active
06329472
ABSTRACT:
Water-soluble or water-dispersible graft copolymers based on a polyvinyllactam, their preparation and use
The invention relates to graft copolymers in which a tert-butyl acrylate and a polymerizable carboxylic acid are grafted onto a polyvinyllactam, to their preparation and to their use, especially in the form of cosmetic preparations, particularly as hair-setting compositions.
A large number of substances have already been described as film formers for cosmetic preparations, in particular for hair cosmetics. The majority are synthetically obtained polymers which are applied to the hair in dissolved form by rubbing in or spraying onto the hair, where they leave behind a transparent colorless film after the solvent has evaporated.
A number of requirements are placed on such substances: the film should adhere firmly to the hair and not flake off or dust off. It should be clear, impart gloss and not be sensitive to moisture so that the treated hairstyle retains its shape, does not stick and bind dust even at high atmospheric humidity. On the other hand, it should be possible to wash out the polymer using a standard commercial shampoo without leaving a residue. Finally, the sprayability of the film former solution requires sufficient solubility of the polymer in the solvents customary for hair treatment compositions and, in the case of application as a spray from a pressurized pack, the problem-free miscibility of the solution with the propellants.
While initially vinyllactam homo- and copolymers were preferentially used, carboxylate-containing polymers have later become increasingly important. The desired profile of properties such as strong hold at high atmospheric humidity, elasticity, wash-off from the hair and compatibility with the other formulation components is achieved by copolymerization of a combination of hydrophobic, elastifying and carboxyl-containing monomers.
Although the above requirements are nowadays achieved by various types of polymer, the feel of hairstyles held using these polymers is being perceived more and more frequently as unpleasantly dull and unnatural. Attempts to achieve an improvement by making additions to the formulations have hitherto led to results which are not entirely satisfactory: although the addition of customary plasticizers does improve the feel, it at the same time reduces the setting action in many cases. The frequently used polysiloxanes are incompatible with the polar polymers and often require further additives in order that they can be formulated at all. Separation out of individual components can lead to problems both during storage of the formulation and during use.
This is true, for example, for the terpolymers described in U.S. Pat. No. 3,405,084, which comprise from 25 to 75% of vinylpyrrolidone, from 20 to 70% of acrylate and from 3 to 25% of acrylic acid.
Improved terpolymers according to EP-A 0 257 444 comprise from 20 to 50% of vinylpyrrolidone, from 40 to 70% of tert-butyl acrylate and from 2 to 15% of acrylic acid or methacrylic acid.
In addition, U.S. Pat. No. 3,594,344 describes graft copolymers for hairspray formulations which have been prepared by grafting a monomer mixture of alkyl acrylates and at least 1% by weight of glycidyl methacrylate onto polymeric N-vinyllactam. A disadvantage of these polymers is, however, not only the toxicity of the glycidyl methacrylate, but also the high crosslinking tendency of this bifunctional monomer. This can lead, for example, to storage instability of the dispersion. Moreover, the epoxide groups of the polymer can form a permanent chemical bond with the proteinaceous substance of the hair and of the scalp. Such polymers cannot be washed out and are rejected as physiologically objectionable.
U.S. Pat. No. 3,770,683 describes emulsion graft copolymers for hairspray formulations which have been prepared by grafting a monomer mixture of (meth)acrylic esters and at least 0.5% by weight of an ethylenically unsaturated monocarboxylic acid onto polymeric N-vinyllactam.
There has then been no lack of attempts to improve the properties of these polymers such that they are less sensitive to moisture and can be used especially in regions with a hot humid climate.
Accordingly, it has already been proposed, according to DE-A 42 02 193, to use emulsion graft copolymers of polyvinyllactams with grafted-on acrylic esters for hair cosmetics. In this connection, it has been found that it is not advantageous to copolymerize monomers containing carboxylic groups, as is described in U.S. Pat. No. 3,770,683, since the neutralization or partial neutralization required for solubility in water does not leave many options, meaning that films are readily obtained which are either difficult to wash out or are soft and sensitive to moisture.
It is an object of the present invention to propose further improved graft polymers which are neither sensitive to moisture nor leave, as a result of their hardness, a flaky residue on the hair when combed out, and which can also be used in a hot and humid climate.
We have found that this object is achieved according to the invention by particular graft polymers, the content of carboxyl-containing comonomers surprisingly not leading to the disadvantages described in DE-A 42 02 193.
Accordingly, the invention provides water-soluble or water-dispersible graft copolymers with a K value of from 30 to 70, obtainable by free-radical polymerization of monomers
(A) consisting essentially of
(a) from 50 to 85% by weight of monomers of the formula I
in which R′ is hydrogen or C
1
- to C
6
-alkyl radicals, and X is the radical
where R″ is hydrogen or a C
1
- to C
6
-alkyl radical, and
(b) from 15 to 30% by weight of a vinyl monomer which has at least one carboxyl group, and, where appropriate,
(c) from 0 to 25% by weight of a free-radically polymerizable vinyl monomer of the formula II
in which R is a C
6
-C
30
-alkyl radical, preferably C
6
-C
22
-alkyl radical, and R′ and X are as defined above, with
B) a prepolymer with a K value of from 30 to 50, comprising, in copolymerized form, at least 30% by weight of monomers of the formula III
in which n is a number from 1 to 3,
the weight ratio A:B being from 100:5 to 100:200, and at least partial neutralization of the graft copolymer.
Component A(a) is preferably an &agr;,&bgr;-ethylenically unsaturated compound of the formula I in which
R′ is hydrogen, methyl or ethyl, and
X is O or NR″, where R″ is hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl or cyclohexyl.
In this connection, it is also possible to use mixtures of compounds of component A(a).
Component A(a) is preferably tert-butyl acrylate, tert-butyl methacrylate, tert-butyl ethacrylate, N-tert-butylacrylamide, N-tert-butylmethacrylamide, N-tert-butylethacrylamide, and mixtures thereof.
Tert-butyl methacrylate is preferable and tert-butyl acrylate is particularly preferable.
Monomers (A)(b) are any, in particular low molecular weight compounds which contain one or more carboxyl-carrying vinyl groups. Specific examples which may be given are acrylic acid, methacrylic acid, fumaric acid, maleic acid, itaconic acid, crotonic acid and mixtures thereof. Preference is given to acrylic acid, methacrylic acid and mixtures thereof.
Suitable monomers (A)(c) of the formula II are, preferably, those in which R′ is hydrogen, methyl or ethyl, X═O or NH, and R is the radicals n-octyl, ethylhexyl, 1,1,3,3-tetramethylbutyl, undecyl, lauryl, tridecyl, myristyl, pentadecyl, palmityl, margarinyl, stearyl, palmitoleinyl, oleyl or linolyl.
The component (A)(c) is chosen in particular from n-octyl (meth)acrylate, 1,1,3,3-tetramethylbutyl (meth)acrylate, ethylhexyl (meth)acrylate, n-nonyl (meth)acrylate, n-decyl (meth)acrylate, n-undecyl (meth)acrylate, tridecyl (meth)acrylate, myristyl (meth)acrylate, pentadecyl (meth)acrylate, palmityl (meth)acrylate, heptadecyl (meth)acrylate, nonadecyl (meth)acrylate, arrachinyl (meth)acrylate, behenyl (meth)acrylate, lignocerenyl (meth)acrylate, cerotinyl (m
Hossel Peter
Kim Son Nguyen
Sanner Axel
Schehlmann Volker
Asinovsky Olga
BASF - Aktiengesellschaft
Keil & Weinkauf
Seidleck James J.
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