JPS6055483B2 - Nail beauty products - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a nail beauty product that has excellent physical properties and is physiologically safe for the skin and nails.

Generally, nail beauty products are mainly made of nitrocellulose, resin,
It is composed of plasticizers, pigments, etc., but it is known that the physical properties of the resin have a great influence on the properties of the coating film, and the suitability of this resin is the key to determining the quality of nail polish. It's summery.

Therefore, this resin must have good compatibility with nitrocellulose, good flexibility, excellent gloss, moderate hardness, and adhesiveness to nails. , has excellent water resistance, is chemically stable, does not cause any change orally, is harmless to the skin and nails, and does not damage the nails with an appropriate removal agent. It is required to satisfy various conditions such as being able to be easily removed without any damage. However, none of the conventionally used resins satisfies all of these requirements. For example, sulfonamide resins used as nail polish resins have excellent physical properties, but
It has the disadvantage that it is chemically unstable, decomposes in the presence of moisture or in high temperature environments, and generates formaldehyde, which has recently raised problems in relation to skin irritation. In addition, there are concerns about the toxicity of phthalic acid-based alkyd resins due to free phthalic acid, and when they are made into products,
Poor flexibility and gloss. Furthermore, linear fatty acid dicarboxylic acid-based alkyd resins are said to be inferior in flexibility, gloss, and water resistance. Furthermore, nail polishes containing acrylic resin have poor adhesion and are easily peeled off. As a result of intensive research aimed at improving the above-mentioned drawbacks, the present inventors have developed a polyester obtained by polycondensing cyclohexane-1,2-dicarboxylic acid, a trivalent or tetravalent alcohol, and a monobasic higher fatty acid. , epichlorohydrin and bisphenol A
The modified polyester obtained by addition reaction with a condensate of The present invention was completed based on the discovery that the resin is superior to the known synthetic resins in terms of heat resistance, light resistance, etc., and is also physiologically safe.

The purpose of the present invention is to produce a coating film that has good pigment dispersibility and compatibility with nitrocellulose, dries quickly, and has excellent physical properties such as gloss, water resistance, flexibility, and adhesive strength, and is also resistant to skin damage. To provide a nail polish that is physiologically safe for nails.

That is, the present invention provides a polyester produced by a polycondensation reaction of cyclohexane 1,2-dicarboxylic acid, a trivalent or tetravalent polyhydric alcohol, and a monobasic higher fatty acid, and a condensate of epichlorohydrin and bisphenol A (hereinafter referred to as This nail beauty product is characterized in that a modified polyester obtained by an addition reaction with an epoxy resin (referred to as an epoxy resin for convenience) is dissolved together with cellulose in an organic solvent.

Embodiments of the present invention will be described below.

Examples of trihydric to tetrahydric alcohols used in the production of the polyester of the present invention include glycerin, trimethylolethane, 1,2,6-hexanetriol, 1,2,3
-butanetriol, 1,2,3-pentanetriol, 2,3,4-pentanetriol, 2,3,4-hexanetriol, 2-isopropyl-2-oxymethyl, 1,3-p-a/dundiol, 1,2,4-butanetriol, 1,2,3,4-tetraoxybutane, 1,
2,3,4-pentatetrol, 2,3,4,5-hexanetetrol, 1,2,3,5-pentatetrol,
Examples include 1,3,4,5-hexanetetrol, 1,6-(3,4)-hexanetetrol, pentaerythritol, diglycerin, and the like.

The ratio of cyclohexane-1●2-dicarboxylic acid to polyhydric alcohol is such that the ratio of carboxyl groups in the dicarboxylic acid to hydroxyl groups in the polyhydric alcohol is 60 to 95.
It is to be made to be equivalent %, more preferably 65 to 90 equivalent %.

If it is less than 60 equivalent %, the degree of polymerization will not increase, the hardness of the resulting resin will be low, and the nail beauty product obtained by blending this resin will be soft and have poor water resistance.

If it is more than 95 equivalent %, the amount of higher fatty acids used at the same time will be too small, and the dispersibility of the pigment added to the nail polish will be extremely poor, and the compatibility with nitrocellulose and flexibility will deteriorate, so it is preferable. do not have.

Examples of monobasic higher fatty acids include monobasic fatty acids with 18 to 20 carbon atoms, such as castor oil fatty acids, hydrogenated castor oil fatty acids, stearic acid, isostearic acid, oleic acid, arachidic acid, arachidonic acid, abietic acid (rosin ), and can be used singly or in combination of two or more.

The appropriate ratio of higher fatty acids to polyhydric alcohol is such that the ratio of carboxyl groups of higher fatty acids to hydroxyl groups of the polyhydric alcohol is 3 to 20% by weight, preferably 10 to 22% by weight. be. Nail beauty products that contain less than 3 equivalent percent of resin are significantly inferior in water resistance, flexibility, and pigment dispersibility, and nail beauty products that contain resin that is greater than 3 equivalent percent have sufficient compatibility with nitrocellulose. Not only that, but the gloss is also inferior.

Note that the ratio of the carboxyl groups of the total fatty acids (cyclohexane-1,2-dicarboxylic acid and higher fatty acids) to the hydroxyl groups of the polyhydric alcohol is desirably less than % by weight.

On the other hand, if the number of carboxyl groups exceeds the amount of hydroxyl groups, the water resistance will be significantly deteriorated when incorporated into a nail polish, which is not preferable. Polyester resin is usually prepared by adding a mixture of cyclohexane-1,2-dicarboxylic acid (anhydride), the above-mentioned higher fatty acid, and polyhydric alcohol in the required amount.
00 acid to 120°C for 1 to 2 hours, and further reacted at 180°C.
It is obtained by reacting at ~200° C. for 2 to 3 hours, and in some cases for 6 to 7 hours. The average molecular weight of the polyester is 1000-2500, preferably 1400-2500.
2200, but if it is less than 1000, the water resistance and hardness of the film will be low, and if it is larger than 2500, the film will have poor flexibility, poor compatibility with nitrocellulose, toluene, etc., and the water resistance will also decrease, so it is preferable. do not have. Modified polyester can be obtained by mixing required amounts of polyester and epoxy resin and heating the mixture to 160 to 185°C to perform an addition reaction.

In this case, the epoxy resin is easily quantitatively added to the active hydrogen of the carboxyl group or hydroxyl group of the polyester,
Its water resistance, hardness and adhesive properties can be improved.

The amount of epoxy resin used is 0.5 to 15% by weight, more preferably 3 to 1% by weight, based on the weight of the polyester.

If it exceeds 15%, the coloration of the modified resin becomes noticeable and the color tone of cosmetics containing it becomes dull, which is not preferable.

The average molecular weight of the epoxy resin is 500 to 140.
0s is preferably 700-1200.

The blending ratio of this resin in cosmetics cannot be specified as a uniform ratio due to the blending amount of nitrocellulose used together, but
-15% by weight is suitable, more preferably 7-12% by weight. If it is less than 5% by weight, adhesive strength and flexibility will decrease, and if it is more than 15% by weight, compatibility with nitrocellulose will decrease, which is not preferable.

The amount of nitrocellulose used is 10-2% by volume.

If it is less than 10%, the gloss tends to decrease.
Moreover, when the amount of saliva is 2%, the compatibility with the resin decreases.

As an organic solvent, usually 20 to 35% by weight of toluene,
5 to 5 saturated monohydric lower alcohols (e.g. ethyl alcohol, isopropyl alcohol, butyl alcohol, etc.)
1% by volume of acetic acid lower alkyl esters (eg ethyl acetate, butyl acetate, etc.) are used.

Further, 2 to 5% by weight of a pigment (dye) and, if necessary, a plasticizer (for example, cyoctyl adipate, etc.) are used. In this case, it is necessary to dissolve nitrocellulose and the modified resin in their respective solvents and mix well, and then to thoroughly mix necessary additives such as pigments and plasticizers. The thus obtained nail polish of the present invention has good pigment dispersibility, dries quickly, and forms a coating film with excellent physical properties such as light resistance, water resistance, flexibility, and adhesive strength. In addition, it is a physiologically safe nail beauty product and has high commercial value.

Examples will be described below.

The test methods for the shine, luster, pencil hardness, flexibility (flexibility), adhesive strength, and water resistance of nail polishes shown in Examples are as follows.

Gloss: Nail polish was applied to a thickness of 80 WLμ on a nylon plate, and after being left at room temperature for 24 hours, the reflectance was measured using a gloss meter at an incident angle of 30 o'clock.

Pencil hardness: Apply nail polish to a thickness of 80TrLμ on a nylon plate, leave it for 1 hour at room temperature, and use a scratch tester to determine the minimum value that can cause scratches on the film under the conditions of a load of 300y and an angle of 45mm. The pencil hardness was measured. B in the table. ．． HB,
．． F. ．． H etc. indicate the hardness of the pencil. Flexibility (flexibility);
A nylon plate coated with nail polish to a thickness of 80 nLμ was bent 180 degrees once every day after coating, and the period until cracks appeared was measured.

．． Note that the sample was left at room temperature during the measurement period. Adhesive strength: Nail polish was applied to a glass plate to a thickness of 100 mμ, and after being left at room temperature for 2 hours, a strong cassero tape was attached to the entire surface of the film, and one end was pulled to measure the stress when the film was peeled off.

Water resistance: Apply nail polish to a thickness of 407nμ on a glass plate, leave it at room temperature for 2 hours, and then apply the nail polish to a thickness of 407nμ.
The degree of whitening of the film was observed after 1 hour.
A case where no change was observed was given a rating of A, and the results were graded into five grades above A depending on the degree of whitening. Example 1 Pentaerythritol 20.4V (0.15 mol),
82 equivalent% (37.8f) (0.245 mol) of cyclohexane anhydride-1,2-dicarboxylic acid based on the hydroxyl group
, castor oil fatty acid 15 equivalent% (26.7f) (0.09
mol) into a reactor (equipped with a thermometer, stirrer, nitrogen gas blowing adapter, etc.), and then allowed to undergo an esterification reaction at 100°C for 1 hour while blowing nitrogen gas.
The temperature was further raised to 180C and the reaction was carried out for 4 hours (while distilling off the water produced by the reaction), resulting in a polyester (
average molecular weight 1450), 5.94y based on its weight
(7% by weight) of an epoxy resin (condensation product of epichlorohydrin and bisphenol A) (dioxirane compound) with an average molecular weight of 900 was mixed and an addition reaction was carried out at 180°C for 2 hours until no epoxy groups were detected. 82.59 was obtained (light brown, transparent, semi-solid at room temperature).

Next, 1% by weight of this modified polyester, 14% by weight of nitrocellulose, and 4.5% by weight of dioctyl adipate dl-
Camphor 3% by weight and butyl acetate 15% by weight, ethyl acetate 12.5% by weight and butanol 2% by weight, isopropanol 4% by weight, toluene 35% by weight, dye 0.1% by weight.
A manicure was produced by blending and mixing well. The sharpness of the dry film of this manicure is 2H or higher (F), the gloss is 98% (72%), the flexibility is 12 days (12 days), and the adhesive strength is 4
00f'Cm (305yIcTn), the water resistance was A (above D), the drying speed was fast, and the pigment dispersibility was excellent (good). (The numbers in parentheses are unmodified polyester, i.e., when epoxy resin is not reacted.) Also, the compatibility with nitrocellulose and organic solvents is compared to ordinary alkyd resins, acrylic ester resins, and sulfonamide resins. It was confirmed that it was significantly superior.

Example 2 Epoxy resin (based on polyester weight) of Example 1
condensate of epichlorohydrin and bisphenol A) (
The addition reaction was carried out in the same manner as in Example 1, except that the proportion of dioxirane compound) was changed to 0.3% by weight, 0.5% by weight, 3% by weight, 12% by weight, 15% by weight, and 2% by weight. was manufactured and its performance was investigated.

The results are shown in Table 1. As is clear from these results, the amount of epoxy resin used is preferably 0.5 to 15% by weight, most preferably 3 to 1, based on the weight of the polyester.

Example 3x The same procedure as in Example 1 was carried out except that the average molecular weight of the epoxy resin (condensate of bisphenol A and epichlorohydrin) was changed as shown in Table 2.

The results are shown in Table 2. 3 In this way, the average molecular weight of the epoxy resin is 500 to 1
400 is preferable, and 700 to 1200 are more preferable.

Example 4 Instead of pentaerythritol, 1,2-propylene glycol (NO.1), glycerin (NO.2),
1,2,6-hexanetriol (NO.3), trimethylolpropane (NO.5), di-glycerin (NO.
6) was esterified in the same manner as in Example 1, except that
Reacted with epoxy resin (dioxirane compound).

The results are shown in Table 3. As described above, trihydric to tetrahydric polyhydric alcohols are excellent as polyols for polyester constituents.

However, divalent alcohols such as 1,2-propylene glycol and sucrose have poor compatibility with nitrocellulose, compatibility with toluene, water resistance, gloss, and flexibility. The specificity of the tetravalent polyhydric alcohol action effect is remarkable. As a comparison 1, phthalic acid-
The performance of conventional resins such as a glycerin type alkyd resin, a succinic acid-glycerin type alkyd resin as Comparative 2, and a polymethyl methacrylate resin as Comparative 3 was similarly examined.

The results are shown in Table 4. Example 5 Myristic acid (N
O. l) Palmitic acid (NO.2) Oleic acid (NO.
3) Isostearic acid (NO.7) Abietic acid (NO.
．． 4) Behenic acid (NO.6) or stearic acid (NO.6)
．． A modified polyester resin was produced by esterification and reaction with an epoxy resin in the same manner as in Example 1, except that 5) was used in the same molar ratio, and a manicure was also prepared in the same manner.

Its performance is shown in Table 5. Thus, as fatty acids in the constituent components of polyester, monobasic higher fatty acids having 18 to 20 carbon atoms are preferred.

Example 6 Using glycerin instead of pentaerythritol,
and cyclohexane-1 for the hydroxyl group of glycerin.
The proportion of 2-dicarboxylic acid was 55 equivalent % (NO.l),
60 equivalent% (NO.2), 65 equivalent% (NO.3), 8
The same procedure as in Example 1 was carried out except that the amounts were changed to 2 equivalent % (NO.4), 90 equivalent % (NO.5), 5 equivalent % (NO.6), and 97 equivalent (NO.7).

The results are shown in Table 6.

In this way, the ratio of cyclohexanone-1,2-dicarboxylic acid to the hydroxyl group of the polyhydric alcohol is 60 equivalent%.
If it is less than , the water resistance will not be sufficient and the hardness will also be low.

Moreover, if it exceeds 95 equivalent %, the flexibility will be poor and the compatibility with nitrocellulose will be poor. Therefore, it is preferably 60 to 90 equivalent %, and most preferably 75 to 90 equivalent %. Example 7 Using glycerin instead of pentaerythritol,
And the ratio of castor oil fatty acid to the hydroxyl group of glycerin is 1 equivalent % (NO.l), 3 equivalent % (NO. 2), 10
Equivalent % (NO.3), 15 equivalent (NO.4), 22 equivalent % (NO.5), 28 equivalent % (NO.6), 30 equivalent %
(No. 7), but the same procedure as in Example 1 was carried out to esterify and react with the epoxy resin.

Its performance is shown in Table 7.

Thus, the ratio of the carboxyl groups of the higher fatty acid to the hydroxyl groups of the polyhydric alcohol is preferably 3 to 28 equivalent %, and more preferably 10 to n equivalent %.

Claims (1)

[Claims] 1 A condensate of epichlorohydrin and bisphenol A is added to a polyester produced by a polycondensation reaction of cyclohexane-1,2-dicarboxylic acid, a trivalent or tetravalent polyhydric alcohol, and a monobasic higher fatty acid. A nail beauty product characterized in that the obtained modified polyester is dissolved in an organic solvent together with nitrocellulose.