KR20070115461A - Luminescent pigment composition for human skin having high luminescence, long afterglow time, high water-resistance and high shape stability - Google Patents

Abstract

A luminescent pigment composition is provided to ensure high afterglow brightness, long afterglow time, high water resistance, and high shape stability after coating, be free of toxicity, and be usable as body paints. A luminescent pigment composition includes 15.0-40.0wt% of a binder resin, 15.0-25.0wt% of a luminescent pigment, 0.1-5.0wt% of a thickener, 25.0-45.0wt% of a shape stabilizer, and the balance of water. The binder resin is at least one selected from the group consisting of poly(vinylpyrrolidone-vinylalcohol) copolymers, polyvinylalcohol resins, copolymers of acrylic acid and methyl (meth)acrylate, and arabic gums. The luminescent pigment is a chemically surface-treated luminescent pigment having water resistance.

Description

Luminescent pigment composition for human skin having high luminescence, long afterglow time, high water-resistance and high shape stability

The present invention relates to a phosphorescent pigment composition, and more particularly to a phosphorescent pigment composition for human application having a high afterglow brightness, long afterglow time, high water resistance and high form stability.

Phosphorescent pigment is a pigment that absorbs and accumulates the energy of natural or artificial light such as sunlight, mercury lamp, fluorescent lamp, incandescent lamp, and then emits the accumulated energy in the form of fluorescence, phosphorescence, etc. in a dark place to emit light. Say. The above-described process of light absorption-energy accumulation-luminescence of the phosphorescent pigment can be repeated without limitation. These photoluminescent pigments were mixed with binder resins and other additives and used as photoluminescent inks, photoluminescent paints, and the like; luminous signs such as switches, outlets, and step slippers; Photoluminescent signs such as guide signs, evacuation tools, emergency exits, stairs, etc .; Ornaments such as ashtrays, necklaces, and earrings; And other items such as fishing tackle, fishing gear, toys, and the like.

On the other hand, as a photoluminescent pigment composition for the purpose of use in the human body there is Korea Patent Publication No. 2006-0037160. It contains 50 to 90 parts by weight of a resin solution, 1 to 3 parts by weight of a trialkylaryl ammonium hectorite fluidizing agent, 0.5 to 3 parts by weight of a silica-based precipitation inhibitor lipophilic with a methyl group (CH3), and photoluminescence It consists of 5 to 50 parts by weight of pigment, 5 to 10 parts by weight of titanium dioxide (TiO ₂ ) as a sieving pigment, 0.1 to 3 parts by weight of photocatalyst (TiO ₂ ), 1 to 10 parts by weight of volatile solvent, 0.5 to 3 parts by weight of inorganic pigment A functional photoluminescent nail polish composition is disclosed. This is to be used for the purpose of coating the keratin nails or toenails as decorative, as can be seen in the term nail polish composition.

However, such a photoluminescent nail polish composition has a solvent such as acetone, ethyl acetate, butyl acetate, methanol, ethanol, volatile organic solvents such as n-propyl alcohol, isopropanol, n-butanol, trialkylaryl ammonium hectorite fluidizing agent, and oxidative photocatalyst. Because it contains a large amount of toxic components such as (TiO ₂ ) to the human body, it is difficult to apply to the surface of the human body. Even if such a composition can be applied to the skin of the human body, such a composition has very poor shape stability and is applied to the surface of the human body in a vertical state exposed to the influence of gravity. Streaming down, the paint for body painting cannot actually be used. In addition, since the shape stability is poor, the fixed form tends to show a problem that the form expressed on the skin is disturbed by friction.

In addition, in order to manufacture a paint for body painting using a conventional photoluminescent pigment, it is advantageous to be an aqueous composition. However, the photoluminescent pigment has a large specific gravity and is poor in dispersibility, so that it is difficult to form an aqueous composition, and thus even an aqueous composition, so-called Oil in Water The high viscosity or solid cream form having an emulsion structure of (W / O) results in poor adhesion and difficulty in fixing, so that it is difficult to express a precise form on the human body.

In addition, such a photoluminescent composition has a short afterglow time as well as a low afterglow brightness, so that there is a lot of improvement when used as a paint for body painting.

Accordingly, an object of the present invention is to provide a photoluminescent pigment composition having a high afterglow luminance and a long afterglow time by solving the above problems of the conventional photoluminescent pigment composition.

Another object of the present invention is to provide a photoluminescent pigment composition having high water resistance and high morphological stability after application.

Another object of the present invention is to provide a photoluminescent pigment composition which can be applied to human skin with no or mild skin toxicity.

The present invention to achieve the above object,

Provided is a photoluminescent pigment composition comprising 15.0 to 40.0 wt% of a binder resin, 15.0 to 25.0 wt% of a phosphorescent pigment, 0.1 to 5.0 wt% of a thickener, 25.0 wt% to 45.0 wt% of a form stabilizer, and a balance of water.

In the photoluminescent pigment composition according to the embodiment of the present invention, the photoluminescent pigment composition may further include 0.1 to 1.0% by weight of a preservative.

In the photoluminescent pigment composition according to the embodiment of the present invention, the binder resin is a poly (vinylpyrrolidone-vinyl alcohol) copolymer, a polyvinyl alcohol resin, a copolymer of acrylic acid and methyl (meth) acrylate, and Arabian At least one selected from the group consisting of gums is preferred.

In the photoluminescent pigment composition according to the embodiment of the present invention, the photoluminescent pigment is preferably a chemically treated water-resistant photoluminescent pigment.

In the phosphorescent pigment composition according to an embodiment of the present invention, the thickener is preferably at least one selected from the group consisting of hydroxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, and carboxymethyl cellulose.

In the phosphorescent pigment composition according to an embodiment of the present invention, the morphology stabilizer is preferably at least one selected from the group consisting of talc, silica, kaolin, and mica.

The photoluminescent pigment composition according to the present invention having the above composition has high afterglow brightness, long afterglow time, high water resistance and high form stability, and also has no human toxicity. Has

Hereinafter, the phosphorescent pigment composition according to the present invention will be described in detail.

Photoluminescent pigment composition according to an embodiment of the present invention is a binder resin 15.0 ~ 40.0% by weight, photoluminescent pigment 15.0 ~ 25.0% by weight, thickener 0.1 ~ 5.0% by weight, form stabilizer 25.0% by weight to 45.0% by weight, and the remaining amount of water Include.

In the photoluminescent pigment composition according to the embodiment of the present invention, the photoluminescent pigment composition may further include 0.1 to 1.0% by weight of preservative, preferably 0.1 to 0.5% by weight. Preservatives that can be used in the present invention include phenoxyethanol, methyl paraben, sorbic acid and the like.

The binder resin is preferably selected from the group consisting of poly (vinylpyrrolidone-vinyl alcohol) copolymers, polyvinyl alcohol resins, copolymers of acrylic acid and methyl (meth) acrylate, and gum arabic. These binder resins may be used alone or in combination of two or more thereof, and in particular, it is preferable to use a transparent one in order to maximize the afterglow effect of the pigment. In particular, the photoluminescent pigment composition of the present invention is particularly intended to be used as a composition for body painting and thus is prepared as an aqueous composition, so that the binder resin should be a water-soluble or at least hydrophilic binder resin excellent in dispersibility in water. Poly (vinylpyrrolidone-vinyl alcohol) copolymers are particularly preferred in this respect.

The content of the binder resin is not particularly limited, but may be 15.0 to 40.0 wt%. If the content of the binder resin is less than 15.0% by weight, the viscosity of the composition is too small, and when applied to the human body there is a fear that the form expressed by the influence of gravity will flow down before it is fixed. If the content thereof exceeds 40.0% by weight, there may be a problem that the viscosity of the composition is too large.

The photoluminescent pigment may be used without particular limitation as long as it is not skin toxic or at least temporary skin toxic. Specific examples thereof include the general formula MO · (nx) [aAl ₂ O ₃ (α) + (1-a) Al ₂ O ₃ (γ)] xB ₂ O ₃ : R [wherein M represents an alkaline earth metal and R represents a rare earth element Where a is 0.5 ≦ a ≦ 0.99, x is 0.001 ≦ x ≦ 0.35, and n is 1 ≦ n ≦ 8.], And the amount of R added is 0.001% to 10% by mol% with respect to M. High brightness long afterglow photoluminescent pigments. The particle size of the photoluminescent pigment is 300-2000 mesh, and the surface color-emitting color range is yellow-yellow, yellow-green, green-green, white-red, red-red.

M may be strontium, R may be europium, and a part of strontium represented by M may be substituted with at least one alkaline earth metal selected from the group of Mg, Ca, or Ba. In addition, a part of the europium represented by R is at least one metal selected from the group of La, Ce, Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Mn, or Bi. Can be substituted. The range of a may be 0.8 ≦ a ≦ 0.9 and x may be 0.05 ≦ x ≦ 0.1.

Specific examples of other photoluminescent pigments that may be used in the present invention are also pigments represented by MAl ₂ O ₄ : Eu, X, wherein M is at least one metal element selected from the group consisting of calcium, strontium, barium, and Eu Is europium as an activator added to 0.001 to 10 mol% of the metal element M, and X is 0.001 to 10 mol% of the activator added to the metal element M, and is at least 1 selected from the group consisting of cerium, yttrium, and ruthenium. More than one element); Alkaline metal aluminate composites revived with one or more rare earth elements selected from the group consisting of small amounts of rare earth metal ions, preferably europium, gadolinium, dysprosium, terbium and ytterbium, more specifically MO.SiO ₂ , Al ₂ O ₃ : Eu (alkaline metal silicate-aluminate oxide doped europium), MO.Al ₂ O ₃ : Eu (alkaline metal aluminate oxide doped europium), where M is calcium, magnesium, strontium At least one member selected from the group consisting of barium, and zinc, and Eu is europium; ZnS: Cu, ZnS: Cu, Cl and the like.

The phosphorescent pigment is used 15.0 ~ 25.0% by weight based on the total weight of the coating composition. When the content of the photoluminescent pigment is less than 15.0% by weight, the density of the photoluminescent pigment in the paint may be too low to obtain sufficient afterglow luminance. When the content exceeds 25.0% by weight, the increase in afterglow brightness is insignificant, but the usability and adhesion are poor, and storage stability may be poor, such as the pigment composition hardening or the pigment settling during storage.

The photoluminescent pigment is free of harmful radiation to the human body when in use, and is preferably at least 7 mcd / m 2 after 60 minutes measured in the manner described below.

The photoluminescent pigment is preferably a photoluminescent pigment having a chemically water-resistant surface treatment in order to increase the water resistance and storage stability. Conventional photoluminescent pigments are weak in water and weaken in brightness when mixed with other components, so that they can not cause serious problems in water resistance when used in aqueous photoluminescent pigment compositions. As a technique for improving the water resistance of a conventional photoluminescent pigment, inorganic particles such as alumina or silica may be used as a photoluminescent pigment. There is a method of coating on the surface of the particles, but the light-treated pigment in the water-resistant treatment of such inorganic particle coating method has a problem in that the coating film is easily ruptured by natural or impact and soon loses the water resistance. Therefore, in the present invention, in order to impart strong water resistance to the photoluminescent pigment, the surface of the photoluminescent pigment is chemically treated to be water resistant, which is preferably used after imparting excellent water resistance. When using a photoluminescent pigment subjected to a water-resistant surface treatment by such a chemical method, it is possible to maintain the performance of emitting light in a dark place without the coagulation even after 10 days to put the photoluminescent pigment composition comprising the same in water. As such, the phosphorescent pigments treated with the water-resistant surface by a chemical method that can be used in the present invention include phosphorescent pigments which can be obtained with water resistance SCR-GWG and GWG 500 from Hualong Yayang, China. On the other hand, if the conventional photoluminescent pigment is not used as the chemically water-resistant surface treatment as it is, the photoluminescent composition is gradually solidified and in most cases it is impossible to maintain the ability to emit light in a dark place after 10 days.

In the photoluminescent pigment composition according to an embodiment of the present invention, the thickener is at least one nonionic or ionic selected from the group consisting of hydroxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, and carboxymethyl cellulose. It is preferred to be a thickener. Examples thereof include Natrosol-250HHR, Tylose HS 30000 YP2 (Clariant), and Viskalex Hv 30.

In the phosphorescent pigment composition according to an embodiment of the present invention, the morphology stabilizer is preferably at least one selected from the group consisting of talc, silica, kaolin, and mica. The form stabilizer is an inorganic particle that does not harm the human body, but the particle size is not particularly limited, but may be about 1 to 50 μm, 5 to 30 μm, and 5 to 20 μm.

Since the composition for human application according to the present invention contains a conventional component in addition to a high brightness afterglow photoluminescent pigment which is an active ingredient, it may contain various components in order to exert a function of a product or to improve a function. Examples of such additives include dispersion stabilizers and preservatives commonly used in the field of the present invention.

Hereinafter, the phosphorescent composition for human application of the present invention will be described in more detail with reference to the following examples. However, these examples are merely illustrative to aid the understanding of the present invention, but the scope of the present invention in any sense is not limited to these examples.

Example  One

After heating 24.6 weight of distilled water to 60 degreeC in beaker, 0.15 g of hydroxypropyl cellulose (manufacturer; AQUALON U.S.A, product number; Natrosol-250HHR) was added, and it stirred well and dissolved. The mixture was cooled to room temperature, 0.25 g of phenoxyethanol was added again, and the mixture was stirred well and mixed uniformly. 25.05 g of talc powder having an average particle diameter of about 17 µm and 30.0 g of silica having an average particle diameter of 13 µm were added to the resultant, and the particles were well dispersed.

Subsequently, a poly (vinylpyrrolidone-vinyl alcohol) copolymer (manufacturer; NOVEON USA, product number; Fixate G-100) was added thereto, stirred and dissolved, and finally, a chemically water-resistant surface treated phosphorescent pigment ( Manufacturer: Hualong yayang, China, product number: GWG 500 water resistance, average particle diameter 25㎛) 15.0g was added, stirred and uniformly dispersed to complete the photoluminescent pigment composition according to the present invention.

Example  2-6

A photoluminescent pigment composition according to the present invention was completed using the same method as Example 1 except for changing the dosage of each component in the content ratio shown in Table 1 below.

TABLE 1 (% by weight)

Ingredient Name Example 1 Example 2 Example 3 Example 4 Example 5 Example 6  water Remaining amount Remaining amount Remaining amount Remaining amount Remaining amount Remaining amount  Hydroxypropyl cellulose 0.15 0.15 0.15 0.15 0.15 0.15  Poly (vinylpyrrolidone-vinyl alcohol) copolymer 25.0 25.0 25.0 30.0 25.0 35.0  Talc 30.0 30.0 30.0 30.0 35.0 25.0  Silica 5.0 5.0 5.0 5.0 5.0 5.0  Phosphorescent Pigment 15.0 20.0 25.0 20.0 20.0 20.0  Phenoxyethanol 0.25 0.25 0.25 0.25 0.25 0.25

Comparative Example 1-7

As shown in Table 2 below, the phosphorescent pigment composition was completed in the same manner as in Example 1, except that at least one dose of each component was changed so as not to fall within the claims.

TABLE 2 (wt%)

Ingredient Name Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7  Purified water Remaining amount Remaining amount Remaining amount Remaining amount Remaining amount Remaining amount Remaining amount  Hydroxypropyl cellulose 0.15 0.15 0.15 0.15 0.15 0.15 0.15  Poly (vinylpyrrolidone-vinyl alcohol) copolymer 25.0 25.0 25.0 20.0 25.0 30.0 -  Talc 30.0 30.0 30.0 20.0 25.0 - 30.0  Silica 5.0 5.0 5.0 5.0 5.0 5.0 5.0  Phosphorescent Pigment 10.0 30.0 - 20.0 20.0 20.0 20  Phenoxyethanol 0.25 0.25 0.25 0.25 0.25 0.25 0.25

Properties of the photoluminescent pigment composition of Example 1-6 and Comparative Example 1-7 were evaluated by the following method.

Afterglow  Measure

Each of the photoluminescent pigment compositions prepared in Examples and Comparative Examples was applied to a substrate of laminated material with a thickness of about 100 μm and completely dried in a room, and then stored for 72 hours in a state of blocking light. Each sample prepared as described above was irradiated with an illuminance of 1000 lux for 30 minutes using 27-watt fluorescence for 30 minutes, and then the change in the afterglow luminance over time was measured in the dark room. The results are shown in Table 3.

TABLE 3

Afterglow after 1 minute (mcd / m ² ) Afterglow after 30 minutes (mcd / m ² ) Afterglow brightness after 60 minutes (mcd / m ² ) Viscosity (cps) Example 1 890 20 8 Example 2 1144 45 15 Example 3 1167 62 19 Example 4 1144 45 15 Example 5 1144 45 15 Example 5 1144 45 15 Comparative Example 1 650 12 6 Comparative Example 2 1327 64 17 Comparative Example 3 - - - Comparative Example 4 1144 45 15 Comparative Example 5 1144 45 15 Comparative Example 6 1144 45 15 Comparative Example 7 1144 45 15

As can be seen from Table 3, it was found that after using the photoluminescent pigment composition according to the present invention, afterglow luminance could be maintained significantly after 60 minutes. Therefore, it was found that the phosphorescent pigment composition of the present invention can sufficiently evaluate a work in a dark place until the end of the event period at the time of body painting event.

Viscosity Stability Measurement

About the photoluminescent pigment composition prepared in Examples and Comparative Examples, the viscosity stability was evaluated under the following conditions.

That is, 70ml of each sample was put in a 100ml round container and stored for 6 hours in a bioincuvator at 25 ℃. After taking it out, the viscosity value 1 minute after the spindle rotation was recorded using Brookfild's viscometer (LV, No. 4 spindle).

Looking at Table 4, the viscosity of the present invention is in the range of 15,000 cps ~ 22,000 cps is a good range to use as a phosphorescent pigment composition for body painting, in the case of the composition of the comparative example is too low to distribute the viscosity in the outside of the range It can be seen that it is very unsuitable for use as a composition for body painting because it is too stiff (difficult to express the form to be expressed in detail).

TABLE 4

Viscosity (cps) Example 1 15,800 Example 2 17,400 Example 3 18,700 Example 4 18,200 Example 5 18,400 Example 6 17,900 Comparative Example 1 11,500 Comparative Example 2 28,600 Comparative Example 3 8,300 Comparative Example 4 12,400 Comparative Example 5 13,300 Comparative Example 6 10,700 Comparative Example 7 11,400

Preservation stability evaluation

The storage stability after leaving the phosphorescent pigment composition prepared in the above Examples and Comparative Examples for 7 days in 45 ℃ oven was evaluated based on the following criteria.

○: No precipitation of pigments, talc, and silica (excellent stability)

(Triangle | delta): The sedimentation of a pigment, a talc, and a silica generate | occur | produces a little (weak stability)

×; Precipitation of pigments, talc, and silica occurs a lot (poor stability)

The results of such storage stability test are shown in Tables 5 and 6 below. While the phosphorescent pigment compositions of Examples 1 to 6, which correspond to the present invention from Tables 5 and 6, have excellent storage stability, the phosphorescent pigment compositions according to Comparative Examples 1 to 7 have precipitated form stabilizers such as pigments and talc after at least 7 days. Since much of this occurred, it was confirmed that the storage stability was poor.

[Table 5] Evaluation of Storage Stability

Neglect time Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 1 day ○ ○ ○ ○ ○ ○ 2 days ○ ○ ○ ○ ○ ○ 3 days ○ ○ ○ ○ ○ ○ 4 days ○ ○ ○ ○ ○ ○ 5 days ○ ○ ○ ○ ○ ○ 6 days △ ○ △ ○ ○ ○ 7 days △ △ △ △ ○ ○

[Table 6] Evaluation of Storage Stability

Neglect time Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 1 day ○ ○ ○ ○ ○ △ △ 2 days ○ △ △ △ ○ △ △ 3 days ○ △ △ △ △ x △ 4 days ○ x △ △ △ x △ 5 days △ x x △ △ x x 6 days △ x x x △ x x 7 days x x x x x x x

When applying the human body  Fixed rating

The fixation property of the composition was evaluated by directly applying to the human belly using the photoluminescent pigment composition prepared in Examples and Comparative Examples. The results are shown in Table 7.

As can be seen from Table 7, in the case of using the photoluminescent pigment composition of Examples 1 to 6 according to the present invention it was confirmed that the body painting operation is easy because the composition does not flow even immediately after applying. On the contrary, when the compositions of Comparative Examples 1 to 6 were used, the composition had a low viscosity and immediately began to flow immediately after application, so that the shape expressed by body painting was not fixed, and thus, body painting could not be performed smoothly.

TABLE 7

Morphology Viscosity (cps) Example 1 Not flowing Example 2 Not flowing Example 3 Not flowing Example 4 Not flowing Example 5 Not flowing Example 6 Not flowing Comparative Example 1 Dripping Comparative Example 2 Although it does not flow down, it is difficult to express in detail Comparative Example 3 Dripping Comparative Example 4 Dripping Comparative Example 5 Dripping Comparative Example 6 Dripping Comparative Example 7 Dripping

As described above, the photoluminescent pigment composition containing the special chemically treated high brightness long afterglow photoluminescent pigment has solved the problem of the photoluminescent pigment composition and has high water resistance and high form stability after application. In addition, since the components used are human-friendly, there is no skin toxicity or may be applied to human skin as it is mild. Especially, it can be suitably used as a paint for body painting, and can be easily washed off with water because it is aqueous. In addition, the photoluminescent pigment composition of the present invention is excellent in long-term storage stability because it is excellent in the resistance to separation due to sedimentation, such as viscosity stability and pigment particle shape stabilizer particles.

Claims (6)

A photoluminescent pigment composition comprising 15.0 to 40.0 wt% of a binder resin, 15.0 to 25.0 wt% of a phosphorescent pigment, 0.1 to 5.0 wt% of a thickener, 25.0 wt% to 45.0 wt% of a form stabilizer, and a residual amount of water. The phosphorescent pigment composition of claim 1, wherein the phosphorescent pigment composition further comprises 0.1 to 1.0 wt% of a preservative. The method of claim 1, wherein the binder resin is at least one selected from the group consisting of poly (vinylpyrrolidone-vinyl alcohol) copolymers, polyvinyl alcohol resins, copolymers of acrylic acid and methyl (meth) acrylate, and gum arabic. Photoluminescent pigment composition, characterized in that the species. The photoluminescent pigment composition according to claim 1, wherein the photoluminescent pigment is a water-resistant photoluminescent pigment chemically treated. The phosphorescent pigment composition of claim 1, wherein the thickener is at least one selected from the group consisting of hydroxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, and carboxymethyl cellulose. The photoluminescent pigment composition of claim 1, wherein the form stabilizer is at least one selected from the group consisting of talc, silica, kaolin, and mica.