Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Processes of preparing a desired or intentional composition...
Reexamination Certificate
2001-01-09
2002-03-19
Michl, Paul R. (Department: 1714)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
Processes of preparing a desired or intentional composition...
Reexamination Certificate
active
06359032
ABSTRACT:
TECHNICAL FIELD
The present invention relates to a polymer emulsion which is useful as a skin cosmetic, a hair cosmetic, a pharmaceutical, a fiber treating agent, a deodorant, an aromatizer, an additive to cement, a coating material, a bactericidal/bacteriostatic agent, an agricultural chemical, etc., to a process for preparing the same and to use of the same.
BACKGROUND ART
Chitosan is a basic polysaccharide obtained by deacetylation of chitin being present in carapace of crustacean animals such as crab and shrimp, treated with a concentrated alkali. However, because of strong hydrogen bond in molecules, chitosan itself is hardly soluble in a solvent other than an acidic aqueous solution and, even it is made into an aqueous solution, viscosity of the solution becomes extremely high whereby its handling is difficult. Therefore, in order to make chitosan into fine particles, a method where chitosan is dissolved in an acid and the resulting solution is gradually dropped into an alkaline coagulating solution as disclosed in JP-A 59-30722, JP-A 62-62827, JP-A 62-70401, JP-A 62-79201 etc., a method where a solution of chitosan or a dispersion of chitosan is mechanically treated as disclosed in JP-A 63-20302, JP-A 63-17902, JP-A 63-210101, etc., and the like are available. However, in all of those methods, only particles in a size of several tens &mgr;m to several hundreds &mgr;m or more are obtained and they are not dispersible in water.
Accordingly, an object of the present invention is to obtain a polymer emulsion where polymer particles of a small particle size containing chitosan are dispersed in water and also to provide use of the said polymer emulsion and of the said polymer particles therein.
DISCLOSURE OF THE INVENTION
The present invention provides a polymer emulsion comprising polymer particles having core-part and shell-part and having an average particle size of not more than 30 &mgr;m, wherein the shell-part is composed of chitosan (a) and a polymer (b) of an organic acid having a reactive vinyl group or a salt thereof as constituent components, and wherein the core-part is composed of a polymer (c) of a hydrophobic monomer as constituent component or is composed of a mixture of the polymer (c) of a hydrophobic monomer and a non-polymerizable hydrophobic substance (d) as constituent component; and provides a process for preparing the same.
The present invention provides a coloring agent particle comprising shell-part composed of a hydrophilic polymer as the constituent component and core-part composed of a hydrophobic polymer as the constituent component, and a coloring material (k) being present in the shell-part and/or the core-part; and provides a hair cosmetic comprising the same.
The present invention provides a deodorizing fiber having a deodorant comprising the following component (S) and the following component (b) on the surface of the fiber; and provides a process for preparing the same;
component (S): a high molecular substance having an amino group,
component (b): a polymer of an organic acid having a reactive vinyl group or a salt thereof.
Incidentally, in the present invention, the term “polymer particle” means a polymer microsphere.
The present invention relates to the above-mentioned polymer emulsion; to a process for preparing the said polymer emulsion; to a polymer particle obtained from the said polymer emulsion; to a coloring agent particle containing the said polymer particles and coloring material included therein; to a hair cosmetic containing the said coloring agent particle; to a hair cosmetic composition containing the said coloring agent particle and a medium such as water and a surfactant; to a fiber deodorant containing the said polymer particle; and to a deodorizing fiber where the said fiber deodorant is present on the surface of the fiber.
The present invention further relates to use of the said polymer particle as a resin for including the coloring material, as a resin for hair cosmetic, or as a deodorizing fiber.
MODE FOR CARRYING OUT THE INVENTION
[1] Process for Preparing the Polymer Emulsion
The polymer emulsion of the present invention can be prepared by the following preparing processes (1) and (2).
Preparing process (1): which comprises emulsifying and dispersing, in water, chitosan (a), an organic acid having a reactive vinyl group or a salt thereof (e) a hydrophobic monomer (f), an oil-soluble polymerization-initiator (g) and, if necessary, a non-polymerizable hydrophobic substance (d), to obtain liquid particles of monomers having an average particle size of not more than 10 &mgr;m and polymerizing the liquid particles, to form core-part and shell-part of the polymer particle.
Preparing process (2): which comprises adding a hydrophobic monomer (f) and, if necessary, a non-polymerizable hydrophobic substance (d) to polymer particles (i) being miscible with the hydrophobic monomer (f) and having an average particle size of not more than 10 &mgr;m, to swell the polymer particles (i), further adding thereto an aqueous solution of chitosan (a) and an organic acid having a reactive vinyl group or a salt thereof (e) and polymerizing the core-part and the shell-part in the swollen polymer particles thus obtained in the presence of an oil-soluble polymerization-initiator (g) and, if necessary, a water-soluble polymerization-initiator (h).
[Chitosan (a)]
The chitosan (a) used in the present invention is a deacetylated product of chitin having the structure of (1→4)-2-acetamido-2-deoxy-&bgr;-D-glucan and has the structure of (1→4)-2-amino-2-deoxy-&bgr;-D-glucan. In the present invention, it may be a chitosan derivative where a part of the deacetylated amino groups or a part of hydroxyl groups in the same molecule is chemically modified such as acylation, etherification, esterification and other reactions. Usually, in the naturally occurring chitin, a part of the acetamido group is an amino group which is not acetylated and, therefore, chitosan which is used in the present invention is that where the degree of deacetylation is 30% or more.
[Organic Acid having a Reactive Vinyl Group or a Salt thereof (e)]
The organic acid having a reactive vinyl group used in the present invention is a water-soluble organic acid which is able to dissolve chitosan to give an aqueous solution and which has one or more reactive vinyl groups and one or more acidic groups in its molecule. Its specific examples include an unsaturated carboxylic acid monomer such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid and maleic acid; an unsaturated sulfonic acid monomer such as styrenesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 3-sulfopropyl (meth)acrylate, bis(3-sulfopropyl) itaconate and vinylsulfonic acid; and an unsaturated phosphate monomer such as vinyl phosphate, bis(methacrylyloxyethyl) phosphate, diphenyl-2-acryloyloxyethyl phosphate, diphenyl-2-methacryloyloxyethyl phosphate, dibutyl-2-acryloyloxyethyl phosphate, dibutyl-2-methacryloyloxyethyl phosphate and dioctyl-2-(meth)acryloyloxyethyl phosphate. One or more of them may be used. Among them, an unsaturated carboxylic acid monomer having a relatively low acidity is preferred and a methacrylic acid having a low acidity in a state of polymer is most preferred.
Examples of the salt of such an organic acid having a reactive vinyl group (e) are alkaline metal salt (such as Na and K salts) and ammonium salt.
It is also possible that, together with the vinyl monomer (e), various acids may be optionally mixed. Examples of the acid to be mixed in this case include an inorganic acid such as hydrochloric acid, sulfuric acid and phosphoric acid and an organic acid such as formic acid, acetic acid, lactic acid, citric acid, tartaric acid, succinic acid, malic acid, oxalic acid, glycolic acid, dichloro acid and trifluoroacetic acid.
[Hydrophobic Monomer (f)]
There is no particular limitation for the hydrophobic monomer (f) which is used in the present invention so far as it is copolymerizable with the above-mentioned organic acid having a r
Akaogi Akira
Hasebe Yoshihiro
Kuwahara Kazuo
Tachizawa Osamu
Takahashi Toshie
Kao Corporation
Michl Paul R.
Oblon & Spivak, McClelland, Maier & Neustadt P.C.
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