JP3392217B2 - Watercolor paint - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to gold or silver watercolor paints containing a pearl pigment (including watercolor paints for posters).

[0002]

2. Description of the Related Art In general, watercolor paints contain coloring pigments; extender pigments such as slight calcium carbonate, clay and alumina silicate; water-soluble polymers such as gum arabic and dextrin; wetting agents such as glycerin; water and the like. Prepared as an aqueous solution. In the case of gold or silver paint, a pearl pigment is included as a coloring pigment. Here, the pearl pigment is a transparent plate-like crystal that forms a layered structure in the coating film and exhibits pearl luster by regularly reflecting, that is, multiply reflecting, incident light in each layer. .

Water-soluble polymers are added as binders to fill the voids between the colored pigment particles in the dried coating.
Extenders such as calcium carbonate and alumina silicate that are commonly used in watercolors have insufficient thickening effect,
It is usually not used in gold or silver watercolor paints because it impairs the shine (glitter feeling) which is a characteristic of pearl pigments.

[0004]

However, in paints containing a pearl pigment, it is generally difficult to satisfy the stability with time by using a thickening agent such as sodium alginate and sodium polyacrylate because the gel tendency is strong and it is difficult. However, if a large amount of these thickeners is used, the glitter feeling is impaired.

The present invention has been made in view of the above technical background, and an object of the present invention is to provide a pearl pigment-containing watercolor paint excellent in stability over time without impairing the glitter feeling. To do.

[0006]

The watercolor paint according to the present invention is
In a watercolor paint containing 5 to 40 parts by weight of a pearl pigment, 0.1 to 5 parts by weight of dioctahedral smectite and 0.01 to 3 parts by weight of trioctahedral smectite are contained as thickeners. Characterize.

As the pearl pigment used in the watercolor paint of the present invention, conventionally known ones can be used without any particular limitation. Specifically, titanium oxide-coated mica, a colored product thereof, iron oxide-coated mica and the like can be used. Of these, titanium oxide-coated mica is in the form of flakes having a high refractive index, has a higher refractive index than coated titanium, is more flaky than mica flakes, and is powdery,
Easy to handle.

The pearl pigment particles have a diameter of 2 to
The thickness is 200 μm, preferably 5 to 100 μm. As for the thickness, the thickness: diameter ratio is preferably about 1: 100 to 1:50. The content of the pearl pigment is 5 to 40 parts by weight, preferably 10 to 30 parts by weight. If it is less than 5 parts by weight, the covering power is insufficient and the glitter feeling is insufficient. If it exceeds 40 parts by weight, it will cause a price increase.

The dioctahedral smectite and the trioctahedral smectite used as a thickener in the present invention are all minerals belonging to the smectite group. Smectites consist of a trilayer structure with two tetrahedral silicate layers on the outside and one hydrated oxide octahedron in the center. Both have a large swelling power and exhibit the effect as a thickener. The difference between dioctahedral and trioctahedral is the difference in the number of octahedral sites in the occupied central layer. In other words, dioctahedral smectites have central cations that are trivalent and divalent substituted. On the other hand, trioctahedral smectite has a monovalently substituted divalent cation.

As the dioctahedral smectite,
It is preferable to use montmorillonite. Montmorillo
Knight has octahedral cation Al replaced by Mg
It belongs to dioctahedral smectite, and the general formula is [(Si
₈(Al_3.34Mg_0.66) O₂₀(OH)_Four] M⁺ _0.66 (M⁺Is Na, Ca and M
at least one selected from the group of g). Mont
Morillonite becomes an emulsion dispersion in an aqueous medium.
In addition, it is possible to disperse water even in the expanded state, producing a thickening effect.
Volatile. On the other hand, montmorillonite forms an emulsified dispersion system.
Therefore, montmorillonite alone can satisfy
It is difficult to obtain stability over time. Satisfaction
In order to obtain time stability, the following trioctahedra
Must be used in combination with

Hectorite is preferably used as the trioctahedral smectite. Hectorite is an octahedral cation Mg replaced with Li, and has a general formula of [(Si ₈ (Mg _5.34 Li _0.66 ) O ₂₀ (OH _, F) ₄ ] M ⁺
_0.66 (M ⁺ is almost all Na). FIG. 1 is a diagram showing a hectorite unit cell. 1 in FIG.
Is an octahedral layer, and 2 and 2 are silicic acid layers. Hectorite may be natural or synthetic, but the general formula in which most of the fluorine in the central layer is replaced by hydroxyl groups is [(Si ₈ (Mg
A synthetic hectorite represented by _5.34 Li _0.66 ) O ₂₀ (OH) ₄ ] M ⁺ _0.66 (M ⁺ is Na) is preferably used.

When hectorite is dispersed in water, the displaceable sodium ions are hydrated and swell to completely separate the platelets. The interaction of these small plates to form a "card structure house" prevents the flow of the water system to exert a thickening effect and prevents the pearl pigment from settling. Furthermore, since it is ionic, the particle / particle bond can be easily broken or regenerated. This is a thixotropic system in which the viscosity is low under shearing force and becomes high when shearing force is removed. Here, thixotropy refers to a phenomenon in which a gel that does not have fluidity in a stationary state reversibly transforms into a sol by applying a mechanical external force and exhibits fluidity. Therefore, since the hectorite particles stick to each other in a stationary state to form a loose structure, they exert a thickening effect and contribute to stability over time. Moreover, when an external force is applied, the card structure breaks and becomes fluid, so the particles of the pearl pigment can be dispersed when applying, and it becomes possible to solidify in a state that they are regularly arranged in layers, preventing the glitter feeling from decreasing. it can. Furthermore, since hectorite gels in the coating film, the coating thickness increases,
The covering power is improved. On the other hand, hectorite causes gelation with an increase in viscosity, which leads to a decrease in leveling as a paint. That is, when the paint is applied with a brush, the elongation of the paint is inferior, and the handwriting is likely to remain after the application, resulting in deterioration of the quality of the paint. It should be noted that hectorite alone cannot satisfy the temporal stability with an addition amount within a range where gelation does not proceed. Therefore, the combined use with the above-mentioned montmorillonite becomes useful.

Therefore, by using the dioctahedral smectite and the trioctahedral smectite together, gelation due to the dioctahedral smectite can be suppressed and both leveling and stability over time can be satisfied. Moreover, since the addition of trioctahedral smectite improves the thixotropy, the deterioration of the glitter feeling due to the increase in viscosity is suppressed, so that both the temporal stability and the glitter feeling can be satisfied.

The content of dioctahedral smectite (preferably montmorillonite) in the watercolor paint of the present invention is 0.1 to 5 parts by weight, preferably 0.5 to 3 parts. This is because if it is less than 0.1 part by weight, the thickening effect becomes insufficient, while if it exceeds 5.0 parts by weight, the dispersion and arrangement of the pearl pigment is hindered and the glitter feeling is deteriorated. When dioctahedral smectite is added only in the above range, the content of trioctahedral smectite (preferably hectorite) is 0.01 to 3 parts by weight,
It is preferably 0.05 to 2 parts by weight. When it exceeds 3.0 parts by weight, not only the thickening effect becomes too large and the glitter feeling is lowered, but also the leveling is deteriorated. On the other hand, 0.0
This is because if it is less than 1 part by weight, the thickening effect will be insufficient and the stability over time will be poor.

The watercolor paint of the present invention preferably contains a water-soluble polymer as a binder for the pearl pigment particles in a dry coating film. As the water-soluble polymer, gum arabic, dextrin, carboxymethyl cellulose,
Polyvinyl alcohol, polyvinyl pyrrolisone, hydroxyethyl cellulose and the like are used. The content of the water-soluble polymer is preferably 1 to 50 parts by weight, particularly 3 to 40 parts by weight. This is because if it is less than 1 part by weight, the fixability is poor, and if it exceeds 50 parts by weight, the amount of the pearl pigment relative to the amount of the binder is relatively reduced and the covering power becomes insufficient.

Further, the watercolor paint of the present invention preferably contains a wetting agent. As the wetting agent, a polyhydric alcohol such as ethylene glycol, propylene glycol or glycerin can be used. The content of the wetting agent is preferably 1 to 15 parts by weight, particularly preferably 2 to 10 parts by weight.
This is because if the amount is less than 1 part by weight, the leveling becomes poor, and if the amount exceeds 15 parts by weight, the drying becomes slow.

If necessary, additives such as a dispersant and a surfactant may be appropriately added to the paint of the present invention. Next, a method for preparing the paint of the present invention will be described. First, a water-soluble polymer, water, a wetting agent, and other additives as needed are added and stirred to prepare a vehicle. Next, dioctahedral smectite and trioctahedral smectite as thickeners are added and stirred. Subsequently, a pearl pigment is added and mixed, and then defoamed to obtain a paint.

In the watercolor paint of the present invention, the pigment volume concentration can be increased by adjusting the content of trioctahedral smectite and reducing the amount of the water-soluble polymer, so that the coating power is required. It can also be applied as a watercolor paint for posters such as poster colors and designer gouache. That is, the present invention can also provide a watercolor paint for posters which satisfies the stability over time and the glitter feeling.

[0019]

EXAMPLES The present invention will be described below based on specific examples. [Example 1] As the dioctahedral smectite, VEEGAUM HV (trade name), which is magnesium montmorillonite manufactured by Vanderlilt, was used. This is montmorillonite, which is obtained by washing inorganic minerals with water, removing impurities and leaving only the ore in a colloidal fraction, and then further purifying this aqueous dispersion, followed by drum-drying into small flakes.

As trioctahedral smectite,
Laponite RD (trade name), a synthetic hectorite manufactured by Laporte Industries Ltd.
Was used. Serogen 6A (trade name of Daiichi Kogyo Seiyaku Co., Ltd.) was used as the water-soluble polymer. This is carboxymethyl cellulose.

As the pearl pigment, Iriodin 300 Gold (particle size: 10 to 60 μm) manufactured by Merck Ltd. was used.
64 parts by weight of water, 6 parts by weight of glycerin as a wetting agent and 2 parts by weight of propylene glycol were added, and the mixture was heated and stirred at about 40 ° C. Serogen 6A was added and dissolved in the aqueous solution. Next, 1.4 parts by weight of dioctahedral smectite and 0.6 part by weight of trioctahedral smectite were added to this solution, and after stirring for about 15 minutes, 20 parts by weight of iridin 300 gold was added as a pearl pigment. And stirred for about 10 minutes. This was defoamed to obtain a golden paint.

With respect to this paint, the glitter feeling, thixotropy, and stability with time were evaluated based on the following methods. Glitter sensation is applied to the concealment test paper, and the glitter sensation after drying is visually evaluated, and ◯ (has a glitter sensation), Δ (slightly inferior glitter sensation), and × (bad glitter sensation)
The grade was evaluated.

The thixotropic paint was packed in a bottle and left for 1 day, then the bottle was tilted and the fluidity of the paint was observed.
The evaluation was made in three grades (slightly flowing) and x (flowing). Stability over time After packing the paint in a bottle and storing it in a thermostatic chamber at 50 ° C for about 1 month, observe the degree of separation of the paint, ○ (no change at all), △ (slightly separated), The evaluation was made in 3 grades of x (large separation or gelation).

[Examples 2 to 4] Addition amount of dioctahedral smectite and trioctahedral smectite,
Further, the types and addition amounts of the water-soluble polymer, the wetting agent, water, and the pearl pigment were changed as shown in Table 1, and the paints of Examples 2 to 4 were prepared in the same manner as in Example 1. Then, with respect to each paint, in the same manner as in Example 1, the glitter feeling, thixotropic property, and temporal stability were evaluated. The evaluation result
The results are shown in Table 1 together with the results of Example 1.

The osmos N (trade name) used in Example 4 is sodium montmorillonite manufactured by Shiraishi Calcium Co. Both serogen 5A and serogen 7A used as the water-soluble polymer are carboxymethyl cellulose manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., and dextrin 101 is a yellow dextrin manufactured by Nitto Kagaku. As the pearl pigment, gold or silver pigments having different particle sizes, which are all commercially available from Merck & Co., Inc. were used. The particle size is as follows.

Iriodin 120 Silver ...... Particle size 5 to 20 μm Iriodin 303 Gold …… Particle size 10 to 60 μm Iriodin 153 Silver …… Particle size 30 to 100 μm
m Iriodin 100 silver ... Particle size 10 to 60 μm As a preservative, Proquel XL-2 (trade name) manufactured by Zeneca was used.

In Table 1, 10% carbon black dispersion means that 6.0 parts of serogen 5A, 6.0 parts of serogen 6A and 2 parts of serogen 7A in 67 parts by weight of water and 9.0 parts by weight of glycerin. After adding and dissolving 1.0 part of carbon black No. 10 parts by weight of 30 (carbon black manufactured by Mitsubishi Kasei) was added, stirred, and then dispersed in a mill. Addition of a small amount of 10% carbon black dispersion gives a dull metallic luster.

[0028]

[Table 1]

It can be seen from Table 1 that all the paints of the present invention satisfy both the glitter feeling and the stability over time. [Comparative Examples 1 to 5] Paints were prepared in the same manner as in Example 1 except that the extender pigments or thickeners shown in Table 2 were used instead of the dioctahedral smectites and the trioctahedral smectites. With respect to the paint, in the same manner as in Example 1, the glitter feeling, thixotropic property, and temporal stability were evaluated. The evaluation results are shown in Table 2.

In Table 2, P820 (trade name) is an alumina silicate manufactured by Degussa, and ASP-170 is E.
MC company Kaolin clay, Rheojic 250H
(Trade name) is sodium polyacrylate manufactured by Nippon Pure Chemical.

[0031]

[Table 2]

As can be seen from Table 2, the paint to which the extender pigment is added does not satisfy the stability over time and has no glitter feeling. In addition, it was not possible to obtain a paint that satisfied both the glitter feeling and the stability over time, using any of the thickeners. Next, the addition amount of dioctahedral smectite and trioctahedral smectite and its effect were investigated.

[Comparative Examples 6 to 11] In the paints of Example 1, the paints of Comparative Examples 6 to 11 in which only the addition amount of montmorillonite or hectorite was changed as shown in Table 3 were prepared, and the paints were carried out. Similar to Example 1,
Glitter feeling, thixotropy, and temporal stability were evaluated. The evaluation results are shown in Table 3 together with the results of Example 1.

[0034]

[Table 3]

As can be seen from Table 3, it is necessary to add hectorite in a predetermined amount or more in order to satisfy thixotropy (Comparative Examples 6, 10, 11). Further, montmorillonite alone (Comparative Example 6) or hectorite alone (Comparative Example 7)
However, even if a predetermined amount is added, the stability over time cannot be satisfied. On the other hand, when either hectorite or montmorillonite is excessive (Comparative Examples 10 and 11), the temporal stability can be satisfied, but the glitter feeling is reduced.

In Comparative Example 8, the stability over time was (x) even when the total amount of the thickener added was 1.45 parts by weight, whereas in Example 4, the total amount of the thickener added was Is 0.9 part by weight, the stability over time is (◯), which indicates that it is necessary to add a predetermined amount or more of laponite for stability over time. In addition, in Example 4, the amount of the water-soluble resin added was large, which also contributed to the increase in viscosity.

[0037]

EFFECT OF THE INVENTION Since the watercolor paint of the present invention contains dioctahedral smectite and trioctahedral smectite as thickeners, it is possible to satisfy stability over time without reducing the glitter feeling. . Further, the paint of the present invention in which a predetermined amount of dioctahedral smectite and trioctahedral smectite are used in combination, has a suitable fluidity when applied, so that the brush is smooth and the handwriting after application is good. It does not remain. That is, the leveling as a watercolor paint is good. Therefore, the present invention can provide gold and silver watercolor paints of stable quality and good quality.

Further, by reducing the amount of the water-soluble polymer, the covering power can be improved without changing the addition amount of the pearl pigment, so that the watercolor paint for posters which requires a covering power such as poster color. Can also be applied to.

[Brief description of drawings]

FIG. 1 is a diagram for explaining the structure of trioctahedral smectite.

[Explanation of symbols]

1 octahedral layer 2 Silica layer

Claims (5)

(57) [Claims] 1. A watercolor paint containing 5 to 40 parts by weight of a pearl pigment, 0.1 to 5 parts by weight of dioctahedral smectite and 0.01 to 3 parts by weight of trioctahedral smectite as a thickener. Partial watercolor paint. 2. A dioctahedral smectite,
The general formula is [(Si8 (Al3.34Mg0.66) O20 (OH) 4] M + 0.66 (M + is
The montmorillonite represented by (at least one selected from the group of Na, Ca and Mg) is used, The watercolor paint according to claim 1. 3. A trioctahedral smectite having a general formula of [(Si8 (Mg5.34Li0.66) O20 (OH) 4] M + 0.66
The watercolor paint according to claim 1 or 2, wherein a hectorite (M + is Na) is used. 4. A trioctahedral smectite having a general formula of [(Si8 (Mg5.34Li0.66) O20 (OH, F) 4] M + 0.66
The watercolor paint according to claim 1 or 2, characterized in that a hectorite of (M + is mostly Na) is used. 5. The watercolor paint according to claim 1, wherein the water-soluble polymer is contained in an amount of 1 to 50 parts by weight.