JPS6111203B2 - - 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. Nail beauty products are generally composed of nitrocellulose as the main ingredient, as well as resins, plasticizers, pigments, etc.
In particular, 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 the resin is the key to determining the quality of nail polishes. However, this resin must have good compatibility with nitrocellulose, be highly flexible, have excellent gloss, have appropriate hardness, be adhesive to nails, and be water resistant. be excellent at;
It is chemically stable, does not change over time, and is harmless to the skin and nails.
It is required to satisfy various conditions such as being able to be easily removed with an appropriate removal agent without damaging the nail. 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 they are chemically unstable and decompose in the presence of moisture or in high-temperature environments. It has the disadvantage of generating formaldehyde which poses problems in connection with irritation. In addition, phthalic acid-based alkyd resins are concerned about toxicity due to free phthalic acid, and when made into products, they lack 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 discovered that cyclohexane-1,2-
A modified polyester obtained by addition-reacting a condensed form of epichlorohydrin and bisphenol A to a polyester obtained by polycondensing dicarboxylic acid, dipentaerythritol, and a monobasic higher fatty acid has excellent gloss, hardness, and pigment miscibility. It is superior to the known synthetic resins in water resistance, abrasion resistance, flexibility, adhesion, drying properties, compatibility with nitrocellulose, heat resistance, light resistance, etc., and is also physiologically safe. They discovered something and completed the present invention. 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 resin produced by a polycondensation reaction of cyclohexane 1,2-dicarboxylic acid, dipentaerythritol, and monobasic higher fatty acid.
Beautiful nails characterized in that a modified polyester obtained by addition reacting a condensate of epichlorohydrin and bisphenol A (hereinafter referred to as epoxy resin for convenience) to Stell is dissolved in an organic solvent together with cellulose. It is a fee. Hereinafter, embodiments of the present invention will be explained in detail. The ratio of cyclohexane-1,2-dicarboxylic acid to dipentaerythritol is such that the ratio of the carboxyl group of the dicarboxylic acid to the hydroxyl group of dipentaerythritol is 60 to 95 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 relatively low (nail beauty products obtained by blending this resin will tend to become soft), and water resistance will tend to decrease.
When the amount is more than 95 equivalent %, the amount of higher fatty acids used at the same time decreases, and the dispersibility of pigments added to the nail polish tends to decrease, and the compatibility with nitrocellulose and flexibility tend to deteriorate. Examples of monobasic higher fatty acids include monobasic fatty acids having 18 to 20 carbon atoms, such as castor oil fatty acids, hydrogenated castor oil fatty acids, hydrogenated castor oil fatty acids,
stearic acid, isostearic acid, oleic acid,
Examples include arachidic acid and arachidonic acid, which may be used singly or in combination of two or more. The usage ratio of the higher fatty acid to dipentaerythritol is appropriately within a range such that the ratio of the carboxyl group of the monobasic higher fatty acid to the hydroxyl group of dipentaerythritol is 3 to 38% by equivalent, preferably 10 to 22%. Equivalent %. Nail beauty products containing less than 3 equivalent% of resin are
Its water resistance, flexibility and pigment dispersibility are relatively low38
If the resin is blended in an amount greater than the equivalent %, the compatibility with nitrocellulose and gloss tend to decrease. The ratio of carboxyl groups in total fatty acids (cyclohexane-1,2-dicarboxylic acid and higher fatty acids) to hydroxyl groups in dipentaerythritol is 98.
It is desirable that it is equal to or less than %. On the other hand, if the amount exceeds 98 equivalent %, and the carboxyl groups are greater than the hydroxyl groups, water resistance tends to decrease when incorporated into a nail polish. The temperature of the polycondensation reaction in the present invention is
100 to 200°C, and preferred embodiments include cyclohexane-1,2-dicarboxylic acid (anhydride),
The mixture of the higher fatty acid and dipentaerythritol in the required amount is reacted at 100-120°C for 1-2 hours, and further reacted at 160-200°C for 2-7 hours. Such an embodiment is preferable because the number average molecular weight of the produced polyester can be easily adjusted and a homogeneous polymer can be produced smoothly. The number average molecular weight of the polyester used in the present invention is preferably in the range of 1,500 to 2,500. If the number is less than 1500, the water resistance and hardness of the film will be low, and if it is more than 2500, the flexibility, compatibility with nitrocellulose, water resistance, etc. of the film will tend to decrease. Modified polyester can be obtained by mixing a required amount of polyester and epoxy resin and heating the mixture to 160 to 185°C to perform an addition reaction. The epoxy resin can be quantitatively easily added to the active hydrogen of the carboxine group or hydroxyl group of polyester, and can improve its water resistance, hardness and adhesiveness. The amount of epoxy resin used is 0.5 to 15% by weight, more preferably 3 to 12% 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 the nail polish containing it becomes dull, which is not preferable. In addition, the number average molecular weight of the epoxy resin is
500-1400, preferably 700-1200. The number average molecular weight of the modified polyester used in the present invention is 1,800 to 4,000, preferably 2,000 to 3,500. If it is smaller than 1800, the water resistance and hardness of the film will be low, and if it is larger than 4000, the film will have poor flexibility, poor compatibility with nitrocellulose, etc., and water resistance will tend to decrease. The amount (content) of modified polyester to be used cannot be specified at a fixed rate due to the amount of nitrocellulose used in combination, but it is 5 to 15% of the total weight of the nail polish.
Weight % is suitable, more preferably 7 to 12 weight %
It is. If it is less than 5% by weight, adhesive strength and flexibility tend to decrease, and if it exceeds 15% by weight, compatibility with nitrocellulose tends to decrease. The amount of nitrocellulose used is 10-20% by weight. If it is less than 10%, the gloss tends to decrease, and if it is 20% by weight, the compatibility with the resin tends to decrease. As an organic solvent, usually 20 to 35% by weight of toluene, aliphatic saturated lower alcohol (e.g. ethyl alcohol),
(propyl alcohol, isopropyl alcohol, butyl alcohol, etc.) and a lower alcohol ester of acetic acid (eg, ethyl acetate, butyl acetate, etc.). In addition, pigment (pigment) and, if necessary, plasticizer (e.g. dioctyl adipate acetyl tributyl citoate, camphor, etc.) 2~
5 weight is 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 nail beauty product of the present invention thus obtained has good pigment dispersibility, dries quickly, and forms a coating film with excellent physical properties such as gloss, water resistance, flexibility, and adhesive strength. It is a physiologically safe nail beauty agent and has high commercial value. In addition, when the modified polyester resin used in the present invention is applied in the form of a film, it has excellent gloss and is superior to conventional polyester resins in terms of hardness, water resistance, abrasion resistance, adhesion, light resistance, etc. In addition to manicure, it can be added to the top coat, which protects the manicure, or the base coat, which improves the adhesion between the manicure and the nails.
Also, since it has good pigment dispersibility, it exhibits excellent effects when used as a resin for paints (for example, base paints, paints for toys, paints for metals, etc.). The present invention will be explained below. % shown in Examples means % by weight. The test methods for the gloss, 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 mμ 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°. Pencil hardness: Apply nail polish to a thickness of 80 mm on a nylon plate, leave it at room temperature for 12 hours, and use a scratch tester to determine the minimum scratch that can cause scratches on the film under the conditions of a load of 300 g and an angle of 45 degrees. Pencil hardness was measured. In the table, B, HB, F, H, etc. indicate the hardness of the pencil. Flexibility (flexibility): 180 nylon plate coated with nail polish to a thickness of 80 mμ once a day after application.
The period until bending and cracking 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 24 hours, strong Sellotape was applied 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 40mm on a glass plate, leave it at room temperature for 24 hours, then remove the glass plate.
The degree of whitening of the film was observed after 12 hours of immersion in water at 20°C. The case where no change was observed was evaluated as A, and the results were graded into five grades from A to E depending on the degree of whitening. Example 1 Dipentaerythritol 25.4g (0.15mol)
and anhydrous cyclohexane to its hydroxyl group.
A reactor (thermometer, stirrer, nitrogen gas blowing adapter etc. After loading the
While blowing nitrogen gas, the esterification reaction was carried out at 100℃ for 1 hour, and the temperature was further raised to 180℃ and the reaction was carried out for 4 hours (while distilling off the water produced by the reaction), resulting in a polyester (number average molecular weight
1700), 5.94g (7% by weight) of its weight
An epoxy resin (condensation product of epichlorohydrin and bisphenol A) (dioxirane compound) with a number average molecular weight of 900 is mixed and an addition reaction is performed at 180°C for 2 hours until no epoxy group is detected.
82.5 g of modified polyester (number average molecular weight: 3000, light brown and transparent, semi-solid at room temperature) was obtained. Next, this modified polyester 10% by weight and nitrocellulose 14
Weight%, acetyltributylcytoate 4.5% by weight, DL-camphor 3% by weight, butyl acetate 15% by weight, ethyl acetate 12.5% by weight, butanol 2% by weight, isopropanol 4% by weight, toluene 35% by weight, dye 0.1% by weight. were mixed well to produce a manicure. The pencil hardness of the dry film of this manicure is over 2H (F), gloss 96% (70%), flexibility
On the 12th (12th), the adhesive strength was 410 g/cm (300 g/cm), the water resistance was A (D to E), the drying speed was fast, and the pigment dispersibility was excellent (good). (The numbers in parentheses are unmodified polyesters, i.e., when epoxy resins are not reacted.) Also, the compatibility of nitrocellulose with organic solvents, etc., is compared to ordinary alkyd resins, acrylic ester resins, and sulfonamide resins. It's noticeably〓〓〓〓
Confirmed that it is excellent. Example 2 Epoxy resin (epichlorohydrin and bisphenol A) relative to polyester weight of Example 1
0.3% by weight, 0.5% by weight, 3
Manicure was produced by carrying out the addition reaction in the same manner as in Example 1, except that the weight percent was changed to 12 weight percent, 15 weight percent, and 20 weight percent, and its performance was examined. The results are shown in Table 1.

[Table] As is clear from this result, the amount of epoxy resin used is 0.5 to 0.5 to the weight of polyester.
15 weight is preferred and 3 to 12 weight is most preferred. Example 3 The same procedure as in Example 1 was conducted 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.

[Table] In this way, the average molecular weight of epoxy resin is 500.
-1400 is preferable, and 700-1200 is more preferable. The performance of prior art resins such as a phthalic acid-glycerin type anhydrous resin as Comparison 1, a succinic acid-glycerin type alkyd resin as Comparative 2, and a polymethyl methacrylate resin as Comparative 3 were similarly examined. The results are shown in Table 4. 〓〓〓〓

[Table] Example 4 Instead of castor oil and fatty acid in Example 1, myristic acid (No. 1), palmitic acid (No. 2), oleic acid (No. 3), isostearic acid (No. 6), behenin Esterification and
A modified polyester resin was produced by reaction with an epoxy resin, and a nail polish was also prepared in the same manner. Its performance is shown in Table 5.

[Table] As described above, monobasic higher fatty acids having 18 to 20 carbon atoms are preferred as fatty acids in the constituent components of polyester. Example 5 Esterification and reaction with an epoxy resin were carried out under the same conditions as in Example 1, and the reaction time was varied while measuring the amount of dehydration to obtain modified polyesters (resins) with different number average molecular weights. Next, a manicure was prepared in the same manner as in Example 1, and its performance test was conducted. The results are shown in Table 6.

[Table] As is clear from this result, the number average molecular weight of the modified polyester is 1800 to 4000, preferably
2000-3500. 〓〓〓〓

Claims (1)

[Claims] 1 cyclohexane-1,2-dicarboxylic acid,
A modified polyester obtained by an addition reaction of a condensate of epichlorohydrin and bisphenol A to a polyester produced by a polycondensation reaction of dipentaerythritol and a monobasic higher fatty acid is dissolved in an organic solvent together with nitrocellulose. A nail beauty product characterized by: