JP3738439B2 - Manufacturing method of nail polish binder, nail polish binder and nail polish - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to nail polish, more specifically, nail polish using a pigment that easily settles, such as pearl pigment and lame agent, and further relates to a binder for nail polish used in these nail polish and a method for producing the same, and belongs to cosmetic technology Is.
[0002]
[Prior art]
Manicure such value Meaning Ruenameru usually hydrocarbons or the film formers toluene, xylene, ethyl acetate, is dissolved in an organic solvent such as ketones such as butyl acetate, is prepared by dispersing a pigment However, using nail polish using such organic solvents may cause damage to the nails and skin, such as roughening, yellowing and loss of gloss, and the solvent is not necessarily safe for the human body. There are various problems with conventional nail polish.
[0003]
[Problems to be solved by the invention]
Therefore, as an alternative to organic solvents in nail polish, water-based nail polish using water or alcohol as the main solvent or acrylic polymer emulsion has been proposed, but they have poor gloss and coating strength. There is a problem that cleaning under alkaline condition is remarkably inferior, viscosity of the thickened nail polish is lowered, and stability of the product is lacking.
[0004]
Furthermore, as a viscosity modifier, it has also been proposed to add a smectite clay mineral to an aqueous nail polish, but it is difficult to disperse the powdered clay mineral itself, and depending on other compounding agents to be added, There are problems such as precipitation and separation of layers and lack of stability over time.
[0005]
In view of the present situation, the inventors have been able to disperse various compounding agents in a stable manner, which is water-based, has a fast drying time, has a coating strength, has little change in viscosity over time, and can be dispersed stably. As a result of diligent research on high-practical value nail polish binders such as pigments and lamellar agents, nail polish binders obtained by mixing alkali-soluble acrylic copolymers and hydrophilic montmorillonite minerals are coated. A pigment that is strong and has a water-based nail polish, requires a fast drying time, has little change in viscosity over time, improves the dispersion stability of other ingredients, and easily settles, such as pearl pigments It was found that the effect of preventing sedimentation was obtained, and the present invention was completed.
[0006]
[Means for Solving the Problems]
That is, the invention according to claim 1 of the present invention is
A vinyl monomer mixture containing 5 to 30% by mass of acrylic acid or methacrylic acid ,
In an organic solvent solution of an alkali-soluble acrylic copolymer obtained by polymerization in an organic solvent,
After adding water in which alkaline substances and hydrophilic montmorillonite minerals are dispersed or dissolved,
A method for producing a binder for nail polish characterized by distilling an organic solvent.
[0007]
The invention according to claim 2 of the present invention is
In the method for producing a nail polish binder according to claim 1,
The amount of the hydrophilic montmorillonite group mineral dispersed or dissolved in the water is
The content is 0.5 to 30 parts by mass with respect to 100 parts by mass of the alkali-soluble acrylic copolymer .
[0008]
The invention according to claim 3 of the present invention is
Prepared by the method for producing a nail polish binder according to claim 1
A nail polish binder characterized by the above.
[0009]
The invention according to claim 4 of the present invention is
A nail polish comprising the binder for nail polish according to claim 3 .
[0010]
DETAILED DESCRIPTION OF THE INVENTION
The nail polish and nail polish binder in the present invention contains an alkali-soluble acrylic copolymer and a hydrophilic montmorillonite group mineral. Hereinafter, the alkali-soluble acrylic copolymer and the hydrophilic montmorillonite group mineral are specifically described. explain.
[0011]
<Alkali-soluble acrylic copolymer>
The alkali-soluble acrylic copolymer has an acid group such as a carboxyl group in the structure, means a copolymer soluble in water in the presence of an alkaline substance, an alkali-soluble acrylic copolymer of definitive to the present invention In the polymer , the monomer constituting the copolymer (hereinafter referred to as “constituent monomer”) is acrylic acid or methacrylic acid (hereinafter referred to as “(meth) acrylic acid” combined with acrylic acid and methacrylic acid). And a monomer copolymerizable with (meth) acrylic acid.
[0012]
Examples of monomers that can be copolymerized with (meth) acrylic acid as constituent monomers of the alkali-soluble acrylic copolymer include the following various vinyl monomers. More than one species of monomer is used.
[0013]
As a specific vinyl monomer,
Unsaturated carboxylic acid monomers or anhydrides or salts thereof;
Unsaturated sulfonic acid monomers such as styrene sulfonic acid and 2-acrylamido-2-methylpropane sulfonic acid or salts thereof;
Unsaturated phosphoric acid monomers such as vinyl sulfonic acid and acid phosphooxyethyl (meth) acrylate, and dialkylamino groups such as (meth) acrylic acid N, N-dimethylaminoethyl and N, N-dimethylaminopropylacrylamide ( (Meth) acrylic esters, acrylamides or methacrylamides;
Styrenes having a dialkylamino group such as N, N-dimethylaminostyrene and N, N-dimethylaminomethylstyrene;
Vinylpyridines such as 4-vinylpyridine and 2-vinylpyridine;
Alkyl halides such as N- (3-sulfopropyl) -N-methacryloyloxyethyl-N, N-dimethylammonium betaine, N-carboxymethyl-N-methacryloyloxyethyl-N, N-dimethylammonium betaine, benzyl halides Quaternized compounds with known quaternizing agents such as alkyl, aryl sulfonic acids, or dialkyl sulfates;
Etc.
[0014]
Furthermore, as other specific vinyl monomers,
(Meth) acrylic acid esters such as methyl acrylate, ethyl acrylate, n-butyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate;
Styrene monomers such as styrene and chlorostyrene;
N-substituted acrylamides such as t-butylacrylamide, methacrylamide;
And acrylonitrile, methacrylonitrile, etc .;
Is mentioned.
[0015]
Alkali-soluble acrylic copolymer definitive to the present invention, as described above, (meth) acrylic acid (meth) acrylic acid and copolymerizable monomer (hereinafter, referred to as "vinyl monomer".) a copolymer of 5 to 30 wt% of the constituent monomer is (meth) are those acrylic acid, those are preferably 10 to 20 wt% (meth) acrylic acid, (meth) If the proportion of acrylic acid is less than 5%, the solubility in alcohol or alkaline water is poor, making it difficult to achieve the object of the present invention. This is not preferable for nail health.
[0016]
Further, the alkali-soluble acrylic copolymer preferably has a glass transition temperature (Tg) of 0 ° C. or higher, and the copolymer having a glass transition temperature of less than 0 ° C. was used for nail polish. In some cases, the coating film may become sticky (adhesive) and may cause adverse effects such as poor adhesion to the nails.
[0017]
The glass transition temperature can be obtained as an actual measurement value by measurement using a DSC apparatus or viscoelasticity. Theoretically, the constituent ratio of the constituent monomers and the known glass of the homopolymer in each monomer Since the copolymer can be designed from the transition point temperature by the following equation 1 and the copolymer can be designed before the polymerization, the value obtained by the calculation by the following equation 1 is used in the present invention.
[0018]
(Formula 1)
100 / Tg = Σ (W _i / Tg _i )
In the formula, W _i is a mass fraction (%) of the constituent monomer I, and T g _i is a glass transition temperature (° K) of a homopolymer of the monomer.
[0019]
The acrylic copolymer comprising the above (meth) acrylic acid and vinyl monomer is prepared by a known polymerization method such as a solution polymerization method, a bulk polymerization method, a precipitation polymerization method using a known radical initiator. However, it is not preferable to use an organic solvent as the material for the nail polish, and since an aqueous binder is desired as the binder, it is prepared by solution polymerization using an organic solvent. , after addition of the polymerization reaction after completion alkaline substance and water, a method of distilling the organic solvent is used.
[0020]
Solution polymerization using an organic solvent is a known method, and a mixture of (meth) acrylic acid and a vinyl monomer is usually used in a water-soluble or water-insoluble organic solvent (for example, isopropyl alcohol). By adding a hydrophobic polymerization catalyst (for example, azobisisobutyronitrile) and polymerizing while stirring at a normal temperature of 50 to 120 ° C., preferably 75 to 90 ° C., the present invention is achieved. The copolymer to be used can be easily prepared. However, if the polymerization temperature is below 50 ° C., it may be avoided because there is a risk of termination of the polymerization reaction or explosion of the polymerization reaction. It is difficult to obtain a copolymer having a degree of polymerization, and the stability of the resulting binder may be impaired.
[0021]
Acrylic copolymer prepared in solution polymerization using an organic solvent, to replace the organic solvent medium is water, to obtain an aqueous solution of the acrylic copolymer, the organic solvent in the solution polymerization, the hydrocarbon It is preferable to use an organic solvent such as alcohol, ketone, ester or ether, or a mixed solvent thereof with water.
[0022]
As a preferable organic solvent,
The boiling point of methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, ethyl acetate, methyl acetate, cyclohexane, n-hexane, n-heptane, acetone, methyl ethyl ketone, toluol, benzol, xylol, etc. is lower than water or with water The solvent which forms the lowest azeotrope can be mentioned, These organic solvents can be used individually or in mixture.
[0023]
Substitution from an organic solvent system to an aqueous system can be performed by a known method, and an alkaline substance is used within a temperature range of 40 ° C. to 90 ° C. while usually stirring an acrylic copolymer and a medium organic solvent. And water are added and the organic solvent is distilled off under reduced pressure .
[0024]
As an alkaline substance,
Known compounds such as ammonia, potassium hydroxide, sodium hydroxide, monomethylamine, monoethylamine, dimethylamine, diethylamine, monoethanolamine, trimethylamine, triethylamine, dimethylethanolamine, diethylethanolamine, triethanolamine, etc. In the present invention, ammonia which is excellent in water resistance of the obtained binder and improves storage stability is preferable.
[0025]
The alkaline substance is added such that the pH of the aqueous medium in which the alkali-soluble polymer is dissolved or dispersed is preferably pH 7 to 10, more preferably pH 7.5 to 8.5. By so neutralizing, the storage stability of the resulting alkali-soluble polymer solution can be increased, and addition of an alkali substance increases the viscosity of the alkali-soluble polymer, so that the alkali-soluble polymer The viscosity can be easily adjusted.
[0026]
Examples of water include tap water, well water, spring water, purified water, alkaline ion water, and the like. Although there is no particular limitation, it is preferable to use purified water or alkaline ion water that is resistant to spoilage.
[0027]
<Montmorillonite minerals>
Hydrophilic montmorillonite is a group of typical mineral constituting the clay, all of which take a three-dimensional structure, a layered silicate compound, generally montmorillonite are beidellite, hectorite, sauconite and the like Can be mentioned.
As said hydrophilic montmorillonite group mineral, the compound which has the general formula shown by the following formula | equation 2 is illustrated.
[0028]
(Formula 2)
_{[(SiO 2) 8 · (MgO} 2/3) a · (OH) 2 / 3a + b-c · F C ] _{^{- b · M y + b /}} y
Wherein the values of a, b, c and y are 0 <a <10, 0 <b ≦ 1, 0 <c ≦ 2 / 3a + b, and 1 ≦ y ≦ 2, and M is an alkali metal ion, alkaline earth And at least one cation selected from the group consisting of metal ions, ammonium ions and amines.
[0029]
This hydrophilic montmorillonite group mineral may be natural or synthetic, and as a commercial product,
Lucentite SWN and Lucentite SWF manufactured by Corp Chemical Co., Ltd.
Laponite B, S, RD, RDS, XLG, XLS made by Laporte
Ben-gel, Ben-gel HV, Ben-gel FW, Ben-gel 15, Ben-gel 23, Ben-gel 31, Bentonite-S, Bentonite-W
Kunipia F, Kunipia G, Kunipia K, Smecton SA manufactured by Kuminine Industries Co., Ltd.
And so on.
[0030]
Among these, preferred are those having good water dispersibility, water swellability, and good transparency. Specifically, Lucentite SWN manufactured by Coop Chemical Co., Ltd. is preferred, depending on the purpose. One or more of these can be selected and used.
[0031]
The hydrophilic montmorillonite group mineral is preferably blended in an amount of 0.5 to 30 parts by weight, more preferably 1 to 30 parts by weight, and still more preferably 1 to 15 parts per 100 parts by weight of the alkali-soluble acrylic copolymer. By blending part by mass, particularly preferably 2 to 10 parts by mass, depending on the type and blending amount of the alkali-soluble acrylic copolymer to be used, the type of nail polish to be used, and the pigments and salts to be included in the nail polish It is preferable to increase or decrease appropriately.
[0032]
To prepare a binder for nail polish from an alkali-soluble acrylic copolymer and a hydrophilic montmorillonite group mineral, a dispersion or solution in which the hydrophilic montmorillonite group mineral is uniformly dispersed in advance with an alkaline substance in water is manufactured. After that, there is a method in which the dispersion or solution is added to and mixed with an alkali-soluble acrylic copolymer in an organic solvent , whereby the nail polish binder of the present invention is prepared.
[0033]
In addition to the above-described components, the nail polish binder of the present invention can be premixed with components that can be used generally for nail polish within a range that does not interfere with the effect.
[0034]
As what can be added and blended, for example,
Oil components such as fats, waxes, hydrocarbons, higher fatty acids, higher alcohols, esters, metal soaps, silicone oils,
Wetting agents, lower alcohols, nonionic surfactants, anionic surfactants, cationic surfactants, surfactants such as amphoteric surfactants,
Powders such as organic pigments, inorganic pigments and powders treated with various oils such as silicones and fluorine compounds,
Pigments such as dyes and natural pigments,
Perfumes such as natural fragrances, synthetic fragrances, blended fragrances,
In addition to special ingredients such as vitamins, hormones, preservatives, UV absorbers, antioxidants, bactericides, plant extracts, animal extracts, enzymes, drugs, acids and alkalis,
Examples include polyhydric alcohols, polymer substances, purified water, pearlizing agents, antifoaming agents, and film forming aids.
[0035]
In addition, as a pigment, pearlizing agent, lame agent,
Carbon black, titanium white (titanium oxide), titanium black, zinc white, red pepper, chromium oxide, iron black, cobalt blue, alumina white, iron oxide yellow, viridian, zinc sulfide, lithopone, cadmium yellow, vermilion, cadmium red, Yellow lead, molybdate orange, zinc chromate, strontium chromate, white carbon, ultramarine, lead white, bitumen, manganese violet, aluminum powder, brass powder and other inorganic pigments, organic pigments and acid dye lake pigments, fish scale foil, coating treatment Various mica titanium such as mica titanium, mica, sericite, mascobite, pearl oyster powder, abalone shell powder, pearl pigment such as Takase shell powder,
Lame agents such as polyethylene terephthalate / polymethylmethacrylate laminate film, polyethylene terephthalate / aluminum / epoxy laminate powder, polyethylene terephthalate / polyolefin laminate film powder, polyethylene terephthalate / gold laminate powder,
Is mentioned.
[0036]
Also, in order to obtain gloss, there is almost no coloring power, generally called extender pigment, and a natural color with transparency is obtained, barite powder, precipitated barium sulfate, barium carbonate, lime carbonate powder, precipitated Calcium carbonate, gypsum, asbestos, clay, silica powder, fine powder silicic acid, light algae, talc, basic magnesium carbonate, alumina white, gloss white, satin white, tricalcium phosphate, hydroxyapatite and the like.
[0037]
Manicure binder of the invention, base coat, and is used in nail polish, such as topcoats for which nail enamels.
[0038]
【Example】
Hereinafter, although the effect of this invention is demonstrated in detail by the manufacture example and Example of an alkali-soluble acrylic copolymer of this invention, this invention is not limited to these.
[0039]
<Production of alkali-soluble acrylic copolymer>
First, solution polymerization was performed at a temperature of 85 ° C. for 12 hours according to the formulation shown in Table 1, and copolymers A to C were produced.
[0040]
【table 1】
In the table, SMA represents stearyl methacrylate, EA represents ethyl acrylate, AIBN represents azobisisobutyronitrile, and IPA represents isopropyl alcohol.
[0042]
<Manufacture of binder for manicure>
After preparing the above copolymer, a nail polish binder was prepared according to the following formulation.
That is, with respect to 100 parts by mass of the copolymer A, the alkaline substance (ammonia water) shown in Table 2 and 5 parts by mass of the hydrophilic montmorillonite group mineral (Lucentite SWN) were uniformly dispersed in 60 parts by weight of water in advance. While adding, IPA was distilled off to obtain a binder for nail polish (binder A) of the present invention.
Thereafter, binders B to E having the compositions shown in Table 2 below were obtained in the same manner as binder A.
Further, ammonia water and water were added to copolymer A to distill IPA, and thereafter 5 parts by mass of lucentite SWN was added and mixed to obtain a binder for nail polish (binder A ′).
[0043]
[Table 2]
[0044]
<Preparation of aqueous nail polish>
Each binder was gradually added and mixed at the composition ratio shown in Table 3, and after confirming that each component was completely mixed, defoaming was performed to prepare an aqueous nail polish.
In Table 3, the lame agent is a polyethylene terephthalate lame agent, the pigment is a red tar pigment, the surfactant is a polyoxyethylene alkyl ether anionic surfactant, and the preservative is a phenol preservative.
The thixotropy, dispersion stability, viscosity stability, and water resistance of the obtained aqueous nail polish were evaluated by the methods shown below. The evaluation results are shown in Table 4.
[0045]
[Table 3]
[0046]
<Method of measuring thixotropy>
BL type viscometer, No. The viscosity was measured at 6 rpm and 60 rpm at a temperature of 25 ° C. after 1 hour of sample preparation with 4 rotors.
When the ratio of the value of 6 rpm / 60 rpm is 1.3 or more, thixotropic property is indicated (◯), and when the ratio is less than 1.3, no thixotropic property is indicated (×).
[0047]
<Evaluation of dispersion stability>
40 ml of each sample is placed in a transparent sample bottle made of glass material with a diameter of 3.3 cm and a height of 8 cm, and the dispersion state of the pearl pigment, lame agent, and binder is visually observed over time (a total of 240 hours every 24 hours). evaluated.
After 10 days, a polymer emulsion that is not separated at all (Good) and dispersibility of a polymer emulsion / pigment is good, but a polymer emulsion that produces separation of 3 mm or more within 10 days is normal (△). A pigment or the like that separated and settled 1 cm or more within one week was evaluated as defective (x).
[0048]
<Evaluation of viscosity stability>
150 g of each sample was placed in a glass bottle having a diameter of 4.3 cm and a height of 12 cm. The viscosity was visually observed over time with 4 rotors (every 24 hours for a total of 240 hours).
When the viscosity change was less than 70% compared to the initial value, (◯), and when the viscosity change was 70% or more, (×).
[0049]
<Evaluation of water resistance>
Each sample was evenly applied to a 0.5 × 15 × 40 mm nylon plate, dried for 1 hour at 25 ° C. and 60% relative humidity, and then immersed in water at 35 ° C. for 1 hour. Then, the presence or absence (white turbidity, swelling, softening, peeling, etc.) of the coating film was visually evaluated.
A coating film with a good state was marked with (◯), a normal coating with (△), and a defective coating with (×).
[0050]
[Table 4]
[0051]
【The invention's effect】
The nail polish binder of the present invention is prepared by adding an alkali-soluble acrylic copolymer obtained by polymerizing a vinyl-based monomer mixture containing 5 to 30% by mass of acrylic acid or methacrylic acid in an organic solvent. After the addition of material and a hydrophilic montmorillonite dispersed or dissolved water, comprising distilling the organic solvent, since the specific alkali-soluble acrylic copolymer and a hydrophilic montmorillonite, safe It has a coating strength, and even if it is water-based nail polish, the time required for drying is fast, the change in viscosity of the water-based nail polish can be prevented, and the dispersion stability of other compounding agents can be improved. Viscosity can be easily adjusted, thixotropic properties can be imparted, and it has an excellent anti-settling effect for pigments that tend to settle, such as pearl pigments and lame agents. .
[0052]
Furthermore, the binder for nail polish of the present invention is excellent in the uniformity of the whole system and the effect of preventing settling, the coating property to the nail is very good, the film obtained after drying is also excellent in the adhesion to the nail and the water resistance, It has a high practical value.
[0053]
Further, the method for producing a binder for nail polish according to the present invention is an organic solvent of an alkali-soluble acrylic copolymer obtained by polymerizing a vinyl monomer mixture containing 5 to 30% by mass of acrylic acid or methacrylic acid in an organic solvent. A binder for nail polish that exhibits the above-mentioned excellent effects is manufactured by a simple means of distilling an organic solvent after adding water in which an alkaline substance and a hydrophilic montmorillonite group mineral are dispersed or dissolved in a solvent solution. Since all processes are performed in a liquid state, management is easy and reaction control is also easy.
[0054]
Furthermore, since the nail polish of the present invention is mainly composed of a nail polish binder having the above-mentioned characteristics, it has a good film forming property and has a constant quality that does not cause separation and precipitation of pigments even after long-term storage. .

Claims (4)

A vinyl monomer mixture containing 5 to 30% by mass of acrylic acid or methacrylic acid ,
In an organic solvent solution of an alkali-soluble acrylic copolymer obtained by polymerization in an organic solvent,
After adding water in which alkaline substances and hydrophilic montmorillonite minerals are dispersed or dissolved,
A method for producing a binder for nail polish characterized by distilling an organic solvent. The amount of the hydrophilic montmorillonite group mineral dispersed or dissolved in the water is
It is 0.5-30 mass parts with respect to 100 mass parts of alkali-soluble acrylic copolymers.
The method for producing a nail polish binder according to claim 1. Prepared by the method for producing a nail polish binder according to claim 1
Nail polish binder characterized by. A nail polish comprising the binder for nail polish according to claim 3 .