JPS6115045B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention involves kneading, heating and compressing (A) organically modified montmorillonite clay and (B) nitrocellulose together with (C) a substance that swells the former and plasticizes the latter,
Gel composition for nail enamel characterized by dissolving and dispersing the chip composition in an organic mixed solvent, a method for producing the same, and a nail enamel characterized by blending these gel compositions. It is. Organo-modified montmorillonite clay, which is used to prevent the separation and precipitation of pigments and pearl materials used in nail enamel, varies markedly in its effectiveness depending on the treatment method used when adding it. There is a drawback that the good gel properties cannot be fully utilized. The present invention is a method for effectively incorporating organically modified montmorillonite clay, known as a non-aqueous gelling agent, into nail enamel to bring out good product stability and coating properties of nail enamel. Conventional known literature describes the use of organically modified montmorillonite clay to prevent precipitation, color separation, and separation of pigments, pearl materials, etc. in nail enamel. (USP3422185) Dispersing a pearlescent luster pigment by mixing and dispersing organically modified montmorillonite clay and an inorganic or organic acid in a cosmetic base. (Japanese Patent Publication No. 47-40375) A gel-like coating composition using an amine-modified montmorillonite clay, a swelling agent such as orthophosphoric acid, and a substance having a polar group and affinity such as acetone, isopropyl alcohol, butyl acetate. (Unexamined Japanese Patent Publication 1973)
-97830) is listed. In these documents, organically modified montmorillonite clay is simply mixed into a nail enamel base, and the resulting nail enamel has poor pigment dispersion stability and poor gloss. This is due to the poor swelling and dispersibility of organically modified montmorillonite clay in nail enamel. Organically modified montmorillonite clay is made by chemically bonding a cationic activator and a polar higher organic compound between the layers of montmorillonite, which is a clay mineral, and becomes swollen when a solvent such as toluene spreads the layers. When the organically modified montmorillonite clay remains as a powder, the montmorillonite particles are in an agglomerated state, and in order to exhibit the original effect in the nail enamel, they must be finely and uniformly dispersed. Mechanical dispersion of organically modified montmorillonite clay into nail enamel using a disper or the like is not enough, and as a result, the nail enamel coating loses its luster and decreases transparency due to aggregated particles of organically modified montmorillonite clay. occurs. Therefore, in order to solve this drawback, the present inventors applied roll treatment, which is one of the pretreatment methods commonly used in the paint industry for the purpose of dispersing pigments, etc., to organically modified montmorillonite, and developed a chip composition. It has been found that by preparing organically modified montmorillonite, the agglomerated state can be eliminated and it can be finely and uniformly dispersed in nail enamel. As a result, nail enamel prepared from a chip composition of organically modified montmorillonite clay showed no loss of gloss or decrease in transparency due to agglomerated particles of organically modified montmorillonite clay, even when it was made into a film. Provides a beautiful coating. In other words, it breaks the conventional concept that clay minerals act as matting agents in addition to exhibiting good gel properties. However, it is not enough that the organically modified montmorillonite clay is finely dispersed in the nail enamel, and unless it is sufficiently swollen by the organic solvent in the nail enamel, good gel properties cannot be achieved. That is, if organically modified montmorillonite clay is simply used as a chip composition, even if it is added to nail enamel, the coating film will have good gloss, but separation and precipitation of pigments will occur, and no stable product will be obtained. (Difference between Example 4 and Comparative Example 4 described later) As a means to solve this drawback, the present inventors have previously developed an organic modified montmorillonite clay, nitrocellulose, with a well-known plasticizer and an organic modified montmorillonite clay that swells well. We have proposed a production method in which a chip composition is prepared by kneading and heating and compressing the powder with an organic solvent, which is then dissolved and dispersed in an organic mixed solvent to prepare a gel composition for nail enamel. (Japanese Patent Application No. 51-62020) When the gel composition prepared by this method is blended into nail enamel, the organically modified montmorillonite clay is finely dispersed by roll treatment, so the coating film has excellent gloss and A nail enamel with good gel properties and excellent pigment dispersion stability was obtained. However, because the organic solvent used scatters in large quantities during roll processing, there are concerns about work hygiene.
Undesirable things. Another drawback is that the concentration of organically modified montmorillonite clay in the gel composition is not constant. In order to compensate for these drawbacks, the present invention uses a substance that swells organically modified montmorillonite clay.
No organic solvents are used; instead, high-boiling non-volatile substances are used. Furthermore, since this material has the plasticizing power of nitrocellulose, a good chip composition can be obtained simply by rolling the organically modified montmorillonite clay, nitrocellulose, and this material together. Roll treatment means heat compression kneading using rolls such as two-stage rolls. The processing temperature is usually 20-70℃,
The pressure also varies depending on the hardness of the chip composition. While most of the solvent used in the patent application 1982-62020 is scattered during the rolling process, the entire amount of the substance used in the present invention enters between the layers of organically modified montmorillonite and remains in a swollen state, taking the form of chips. It's on. Therefore, in the next step (the step of dissolving and dispersing the chip composition in an organic mixed solvent), the mixed solvent can easily enter between the layers of organically modified montmorillonite clay, resulting in good nails containing plenty of the mixed solvent between the layers. A gel composition for enamel is produced. Therefore, even in nail enamel using this gel composition, the organically modified montmorillonite clay remains in a well-swollen state and exhibits good gel properties, with no separation or sedimentation of pigments or pearlescent agents observed at all. Also, since it is made fine by roll processing, the gloss of the coating film is also very beautiful. In the present invention, the substances that can sufficiently swell the organically modified montmorillonite clay and plasticize the nitrocellulose are as follows. (1) Glycol represented by the general formula HO(RO)nH However, R: C ₂ H ₄ n: 3-90 (2) Ether represented by the general formula R′O(RO)nH However, R: C ₂ H ₄ R′: Straight chain alkyl group with 12-18 carbon atoms n: 8-15 (3) Ester represented by the general formula R″OOC(CH ₂ )nCOOR″ However, R″: Straight chain with 2-4 carbon atoms Alkyl group n: 4-8 The power of these substances to swell dimethylbenzyldodecylammonium montmorillonite clay (trade name Bentone 27) (a) and the power to plasticize nitrocellulose and resin (b) are listed in Table 1.
It will look like this.

【table】

[Table] The measurement methods for (a) and (b) are as follows. (a) According to the recipe in Table 2 (), roll treatment is performed using bentone 27, nitrocellulose 1/4 sec, and these substances to prepare a chip composition, and the organically modified montmorillonite clay in this chip composition is The interlayer distance (OOl) plane is measured using X-rays. (Rigaku Rota slex RU-3 type). Furthermore, Benton
The interlayer distance of the 27 powder was 9.4A. Benton
It can be seen that the interlayer distance is wider for chips made of a material that swells 27 better. For reference, for substances that have the force (a) but not the force (b), prepare a chip composition according to the recipe in Table 2 () and perform X-ray measurement in the same manner to measure the interlayer distance. did. Furthermore, DBP has confirmed that it is not involved in any way between the layers of Benton 27.

[Table] (B) Prepare an enamel base according to the recipe in Table 3, apply a coating film to a thickness of 0.175 mm on a glass plate using an applicator, and measure the hardness after 1 hour using a Vitsukas hardness meter. The larger the value, the softer the coating film.

[Table] * Vitsukas hardness meter A microhardness meter manufactured by Akashi Seisakusho (model: -
MVK). The test was carried out according to the Japanese Industrial Standards Bitskers Katasa test method under the following conditions. Paint film thickness 0.175mm Load 100 gr Load holding time 5 seconds From Table 1, for (a), for 16Å or more (b), for
If it is 110 or more, it is a necessary and sufficient condition as an additive substance during roll processing of the present invention. In addition, ethylene glycol monobutyl ether,
If it takes a large value for (a) but a small value for (b), such as benzyl alcohol, it can be used in combination with a known plasticizer (e.g. DBP) as in the formulation in Table 2 (). A chip composition may be prepared. This is the technology of patent application No. 51-62020. Conversely, in cases where (a) takes a small value and (b) takes a large value, such as butyl carbitol acetate and diisobutyl adipate,
Although it may be a good plasticizer, there is no point in adding it to the chip composition of the present invention. The organic mixed solvent used when dissolving and dispersing the chip composition to prepare the gel composition may be any solvent that constitutes nail enamel, but organically modified montmorillonite in the chip composition may be used. Solvents such as toluene and xylene are essential for further swelling the clay, and solvents such as ethyl acetate and butyl acetate are essential for dissolving nitrocellulose. In addition, there are also ketone solvents such as methyl ethyl ketone and alcohol solvents such as ethyl alcohol and propyl alcohol, and a mixed solvent appropriately blended depending on the type of organically modified montmorillonite clay and nitrocellulose used is used. The chip composition contains (A) 25 to 70% by weight of organically modified montmorillonite clay, and (B) 5 to 70% by weight of nitrocellulose.
From the above various results, it has been found that a range of 70% by weight and 5 to 30% by weight of the substance that swells (A) and plasticizes (B) has a satisfactory effect as a gel composition. Next, specific examples of gel compositions will be shown. The blending amount is in weight%. Example 1

[Table] (Mixed solvent part) Isopropyl alcohol 19 Toluene 39 N-Butyl acetate 42 Total 100 After mixing each component of the chip composition, the chip composition is prepared by heating and compressing with a two-stage roll. 18% of this chip composition and 82% of the prepared mixed solvent are mixed and dissolved and dispersed to obtain a gel composition. Comparative example 1

【table】

[Table] After dissolving 1/4 second of nitrocellulose in a mixed solvent of isopropyl alcohol, toluene, and n-butyl acetate, polyethylene glycol (molecular weight
300) and dimethylbenzyldodecylammonium montmorillonite and mix to obtain a homogeneous gel composition. The final formulation of the gel composition is the same as in Example 1. Comparative example 2

[Table] (Mixed solvent part) Isopropyl alcohol 19 Toluene 39 n-Butyl acetate 42 Total 100 After mixing each component in the chip composition, the chip composition is prepared by heating and compressing with two-stage rolls.
This chip composition 18% and prepared mixed solvent 82%
and dissolve and disperse to obtain a gel composition. This gel composition uses a known plasticizer DBP in place of polyethylene glycol (molecular weight 300) in the formulation of Example 1. Example 2

[Table] (Mixed solvent part) Isopropyl alcohol 18 Toluene 38 n-butyl acetate 44 Total 100 After mixing each component in the chip composition, the chip composition is prepared by heating and compressing with two-stage rolls.
18% of this chip composition and the prepared mixed solvent are mixed and dissolved and dispersed to obtain a gel composition. Example 3

[Table] (Mixed solvent part) 3 Isopropyl alcohol 17 Toluene 45 N-Butyl acetate 38 Total 100 After mixing each component in the chip composition, the chip composition is prepared by heating and compressing with two-stage rolls.
This chip composition 18% and prepared mixed solvent 82%
and dissolve and disperse to obtain a gel composition. Table 4 shows physicochemical comparative data between the gel composition of the present invention and a conventional mixture.

【table】

[Table] It was found that the gel compositions of the present invention (Examples 1, 2, and 3) were better than Comparative Example 1 in both gloss and transmittance. The reason why the glossiness and transmittance of Example 1 are slightly inferior is due to the difference in the grade of organically modified montmorillonite clay.Also, the reason why the glossiness and transmittance of Comparative Example 2 is good is that of Examples 1 and 2. This is because the roll treatment is performed in the same manner as in 3. Next, Table 5 shows specific examples when the gel composition of the present invention is blended into nail enamel. An example is also shown in which the nail enamels prepared using Examples 1, 2, 3 and Comparative Example 2 with high gloss and transparency (Examples 4, 5, 6 and Comparative Example (4) are all However, although Comparative Example 4 had good gloss, it did not show good gel properties (thixotropic properties), and the pigments and pearlescent materials precipitated, making it extremely stable. This is a bad nail enamel.This is because, as has been detailed so far, the chip composition in Comparative Example (1) was not prepared using a substance that swells organically modified montmorillonite clay.

【table】

[Table] Examples 4, 5, and 6 all exhibited good gel properties, and the pigments and pearl materials did not settle at all, making them extremely stable nail enamels. In addition, Comparative Example 3, which was formulated with Comparative Example 1 which had poor gloss and transparency, was a nail enamel with poor coating film gloss and gel properties.

Claims (1)

[Claims] 1 (A) Organically modified montmorillonite clay 25-70% by weight (B) Nitrocellulose 5-70% by weight (C)(1) Glycol represented by the general formula HO(RO)nH However, R: C ₂ H ₄ n: 3-90 (2) Ether represented by the general formula R′O(RO)nH However, R: C ₂ H ₄ R′: Straight chain alkyl group having 12-18 carbon atoms n: 8- 15 (3) Ester represented by the general formula R″OOC(CH ₂ )nCOOR″ However, R″: Straight chain alkyl group with 2-4 carbon atoms n: One or more types of 4-8 5-30% by weight 10-30% of the chip composition obtained by heat-compression kneading using a roll and an organic mixed solvent.
A gel composition for nail enamel obtained by dissolving and dispersing 90-70%. 2 The chip composition is (A) dimethylbenzyldodecylammonium montmorillonite, (B) nitrocellulose 1/4 second, (C) polyethylene glycol (molecular weight
300) A gel composition for nail enamel according to claim 1, which is a chip composition comprising: 3 Claims in which the chip composition is a chip composition consisting of (A) dimethylbenzyldodecylammonium montmorillonite, (B) nitrocellulose 1/2 s, and (C) polyoxyethylene stearyl ether (number of moles of EO added is 9) The gel composition for nail enamel according to item 1. 4. The gel for nail enamel according to claim 1, wherein the chip composition is a chip composition consisting of (A) dimethyldioctadecylammonium montmorillonite, (B) nitrocellulose 1/2 sec, and (C) diethyl adipate. Composition. 5 (C) is polyethylene glycol (molecular weight 300~
4000) The gel composition for nail enamel according to claim 1. 6. The nail enamel gel composition according to claim 1, wherein (C) is polyoxyethylene lauryl ether (E0 addition mole number: 8-15). 7. The gel composition for nail enamel according to claim 1, wherein (C) is polyoxyethylene stearyl ether (9-15 moles of EO added).