JP2003221552A - Color-changeable glossy drawing material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a color-changeable glossy drawing material which has a clear gloss and changes the color of drawn mark depending upon a visual angle in a drawing material, for example, a water-soluble drawing material such as a water color, acrylic paint, etc., a solid drawing material such as a crayon, a pastel crayon, etc. <P>SOLUTION: In this water-soluble drawing material comprising at least pearlescent pigment, a water-soluble resin or resin emulsion and water or in this solid drawing material comprising at least the pearlescent pigment and wax, a pearlescent pigment having 42-68% coating ratio of titanium oxide to mica is used as the pearlescent pigment. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to glossiness such as pearl and metallic to the drawing surface of drawing materials such as water-soluble drawing materials such as watercolor paints and poster colors, solid drawing materials such as crayons and passes, and the visual angle. The present invention relates to a discoloring gloss drawing material that gives a visual effect such that the color of the drawing surface changes.

[0002]

2. Description of the Related Art Conventionally, a glossy coloring material called a pearl pigment has been used as a drawing material for obtaining a drawing surface having a pearl or metallic luster, but it is simply white silver, gold, red, copper. It only shows luster such as color and green.

The pearl pigments include natural products such as fish scale foil, basic lead carbonate, bismuth oxychloride, natural mica coated with metal oxide, and synthetic mica coated with metal oxide. There are synthetic products such as things.
The above-mentioned conventionally used pearl pigments are often used in terms of availability and safety, in which the surface of natural mica is coated with a metal oxide or the surface of synthetic mica is coated with a metal oxide. ing. The color tone of the pearl pigment mainly depends on the kind of the metal oxide coated on the surface. For example, a metal oxide containing 10 to 40% of titanium oxide or aluminum oxide has a white silver tone.
Further, those using iron oxide (coverage 20 to 50%) or those provided with a titanium oxide layer (coverage 10 to 40%) and iron oxide layer (coverage 4 to 37%) are iron oxide layers. Due to the absorption of a part of the wavelength region, the color tone becomes gold, red, and copper.

[0004]

The pearl pigment used in the above prior art has a certain degree of transparency,
The light reflected at the interface between the high index metal oxide layer and the low index mica and surrounding media provides a pearlescent luster. That is, a part of the incident light is reflected, while its complementary color is transmitted, and becomes a reflected color and a transmitted color, respectively. Therefore, when the surface to be drawn is white paper with total reflection, the complementary color that is the transmissive component is reflected back to the original by the surface to be drawn and added to the component that is the originally reflected color, reducing the color effect. As a result, there is a problem that the transparency of the drawing marks is poor due to the transparency. In particular, when used on a white surface to be drawn, it was difficult to distinguish a drawing mark due to reflection on the paper surface. Although it can be solved to some extent by adding a coloring material such as a pigment, the glossiness of the pearl pigment becomes insufficient. Especially in the case of paint, the viscosity is high, so if a large amount of colorant is added, most of the colorant on the surface of the pearlescent pigment will be covered with the colorant and the glossiness of the pearlescent pigment will be impaired. However, in order to maintain the glossiness of the pearl pigment, it is a trace of drawing which is substantially thin. Moreover, the color tone of the handwriting was a constant color from any angle. The present invention provides a discoloring glossy drawing material that provides a drawing trace that maintains glossiness and has a high density, and that has a characteristic that a visible color differs depending on a viewing angle, that is, a viewing angle. Is an issue.

[0005]

DISCLOSURE OF THE INVENTION The gist of the present invention is a discoloring gloss drawing material comprising at least a pearl pigment having a titanium oxide coverage of 42% or more and 68% or less and a fixing agent. To do.

The present invention will be described in detail below. The pearl pigment used in the discolorable glossy drawing material of the present invention is used for the purpose of imparting a change in the color of handwriting depending on the viewing angle.

The pearl pigment used in the present invention has a titanium oxide coverage of 42% or more and 68% or less. The pearl pigment reflects light in a part of the wavelength region of the incident light depending on the film thickness of the titanium oxide layer, while transmitting light in the wavelength region corresponding to its complementary color, and becomes a reflected color and a transmitted color, respectively. For example, when the coverage of titanium oxide is 42%, the reflection color is gold and the transmission color is blue, when it is 47%, the reflection color is purple and the transmission color is yellow green, and when it is 52%. The reflection color is blue and the transmission color is yellow, and in the case of 68%, the reflection color is green and the transmission color is magenta. When the coverage of titanium oxide is less than 42%, the color tone is white silver, and the transparency is low, the hiding power and the coloring power are low, and the visibility of drawing marks is extremely low, and the titanium oxide coverage is 68%. Beyond that, the hiding power becomes stronger, the luster becomes weaker, and the pigment becomes a mere white pigment, resulting in a constant color from any angle.

Commercially available pearl pigments include Ir
iodin 205 RutilePlatinum
Gold (Titanium oxide coverage 43%, particle size 10-60
μm), 215 Rutile Red Pearl
(47%, particle diameter 10-60 μm), 219 Ru
tile Lilac Pearl (48%, particle diameter 10-60 μm), 225 (52%, particle diameter 10-)
60 μm), 235 (57%, particle size 10-60 μm)
m) (above, manufactured by Merck Japan Ltd.) and PEARL
-GLAZE MB-100R (Titanium oxide coverage 52
%, Particle diameter 10 to 60 μm), the same MG-100R (the same 5
7%, particle diameter 10-60 μm), MR-100R (same as 4
7%, 10 to 60 μm), the same MV-100R (the same 48
%, Particle size 10-60 μm), MRB-100R (47%, particle size 10-60 μm), MY-100R
(43%, particle size 10-60 μm), MB-100
RF (62%, particle size 5 to 30 μm), MG-10
0RF (65%, particle size 5-30 μm), MRB-
100RF (56% of same, particle size 5 to 30 μm), MY
-100RF (57%, particle size 5-30 μm), M
B-2100R (51%, particle size 10 to 60 μm),
The same MG-2100R (68%, particle size 10-60μ)
m), the same MV-2100R (47%, particle size 10-6)
0 μm), MR-2100R (45%, particle size 10)
~ 60 μm), the same MRB-2100R (61%, particle diameter 10-60 μm), the same MY-2100R (42%, the same).
Particle diameter 10-60 μm) (above, Nihon Koken Kogyo Co., Ltd.)
Made). These pearl pigments can be used alone or in combination of two or more kinds. In the case of a pearl pigment, since gloss appears due to regular multiple reflection on parallel surfaces having different refractive indexes, the gloss becomes weak when the particle diameter is smaller than 5 μm. Therefore, the particle size is preferably 5 μm or more. Further, it is desirable that the particle diameter is 60 μm or less. This is because if the particle size is larger than 60 μm, the elongation and touch at the time of drawing are deteriorated. The pearl pigment used in the present invention can be used in an amount of 10 to 50% by weight, preferably 20 to 40% by weight, based on the total amount of the discoloring glossy drawing material.

As the fixing agent used in the present invention, when the discolorable gloss drawing material is a fluid water-soluble drawing material such as a paint, a water-soluble resin or resin emulsion is used, and the drawing material is a crayon or a paste. In the case of such solid drawing material, wax is used.

Water is used as the main solvent for the water-soluble drawing material.

The water-soluble resin includes natural resins such as gum arabic, tragacanth gum, dextrin and glue, synthetic resins such as polyvinyl alcohol, semi-synthetic resins such as carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, ammonium polymethacrylate and polymethacrylate. Examples thereof include alkali-soluble acrylic resins such as acrylate ammonium salts and acrylate methacrylic acid ester copolymer alkali salts. These water-soluble resins may be used alone or in admixture of two or more, and the amount thereof is preferably 5 to 30% by weight based on the total amount of the water-soluble drawing material. This is because if the amount of the water-soluble resin used is less than 5% by weight with respect to the total amount of the water-soluble drawing material, a sufficient fixing effect cannot be obtained, and if it is more than 30% by weight, the drawing characteristics deteriorate.

The resin emulsion is used as a water-resistant fixing agent for paints, and includes methyl methacrylate, methyl acrylate, ethyl acrylate, ethyl methacrylate,
Isopropyl acrylate, isopropyl methacrylate,
Examples thereof include ester emulsions such as butyl acrylate and butyl methacrylate, emulsions of copolymers in which the above-mentioned acrylic acid esters and methacrylic acid esters are combined, and styrene-acrylic acid ester copolymer emulsions. The amount used is preferably 5 to 30% by weight (solid content) with respect to the total amount of the water-soluble drawing material. The amount of resin emulsion used is based on the total amount of water-soluble drawing material.
This is because if it is less than 5% by weight, a sufficient fixing effect cannot be obtained, and if it is more than 30% by weight, the drawing characteristics are deteriorated.

The wax is used for forming a solid drawing material in addition to a function as a fixing agent, and it is an animal wax such as beeswax, spermaceti or white wax, candelilla wax, carnauba wax. , Natural wax such as plant wax such as wood wax, montan wax, mineral wax such as ozokerite, petroleum wax such as paraffin wax and microcrystalline wax, Fischer-Tropsch wax, low molecular weight polyethylene and derivatives thereof, montan wax, Derivatives of paraffin wax and microcrystalline wax,
Examples thereof include synthetic waxes such as cetyl alcohol, stearic acid, polyethylene glycol stearate, and castor wax. These waxes can be used alone or in admixture of two or more, and the amount thereof is preferably 10 to 60% by weight based on the total amount of the solid drawing material.

The water-soluble high-boiling point solvent is used for the purpose of adjusting the drying of water-soluble drawing materials, antifreezing agents, etc.
Specifically, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol,
Dipropylene glycol, polyethylene glycol,
1,3-butylene glycol, thiodiethylene glycol, 1,5-pentanediol, glycols such as glycerin, ethylene glycol monomethyl ether,
Diethylene glycol monomethyl ether, 2-pyrrolidone, N-methyl-2-pyrrolidone, triethanolamine and the like can be used alone or in admixture of two or more. The amount used is based on the total amount of water-soluble drawing material.
0.5 to 10% by weight is preferable.

In both the water-soluble drawing material and the solid drawing material, if necessary, carbon black, titanium oxide, iron black, ultramarine blue, red iron oxide, zinc oxide, other than the above-mentioned components, may be used as colorants. Inorganic pigments and organic pigments such as phthalocyanine blue, phthalocyanine green, watching red, carmine 6B, and Hansa yellow can be used, and they may be used alone or in combination of two or more. The amount used varies greatly depending on the type of pigment, but in consideration of color development and drawability, it is 0.
5-10% by weight is preferred. In addition, extenders such as kaolin, talc, calcium carbonate, silica, barium sulfate, resins such as polyethylene, polypropylene, polyvinyl chloride, thickeners, preservatives, antifungal agents, defoamers, surfactants, etc. Of course, they can be used in combination.

When the discolorable glossy drawing material of the present invention is a water-soluble drawing material, it can be easily obtained by mixing and dispersing the above components in a conventionally known disperser such as a three-roll mill, a horizontal ball mill or a horizontal bead mill. be able to.
In the case of a solid drawing material, the above components are heated and mixed with stirring, and if necessary, kneaded with a kneader such as a kneader or a roll mill, and then poured into a mold in a molten state, or injection / pressurization or extrusion. It can be obtained by cooling and solidifying.

[0017]

The pearl pigment used in the discoloring glossy drawing material according to the present invention has a titanium oxide coverage of not less than 42% and not more than 68%, and thus exhibits different reflected and transmitted colors. Further, the water-soluble resin, resin emulsion, and wax used as the fixing agent make the coating film drawn by the drawing material opaque in order to refract and scatter light. For this reason, even if the surface to be drawn is white paper with total reflection, the complementary color of the transmission component is
The reflected color is not reflected by the surface to be drawn, and the reflected color can be clearly recognized. At a viewing angle where the reflected color cannot be recognized, the complementary color that would otherwise be transmitted can be recognized due to the refraction of the fixing agent. Further, even when used on a white surface to be drawn, it becomes easy to distinguish a drawing mark. For this reason, it becomes a discoloring gloss drawing material that obtains glossiness such as pearly tone or metallic tone on the drawing surface and a visual effect that the color of the drawing surface changes depending on the viewing angle.

[0018]

【Example】

The above components were put in a lab mixer and mixed by stirring for 60 minutes to obtain a water-soluble drawing material (watercolor paint).

[0019] The above components were put in a lab mixer and mixed by stirring for 60 minutes to obtain a water-soluble drawing material (watercolor paint).

[0020] The above components were put in a lab mixer and mixed by stirring for 60 minutes to obtain a water-soluble drawing material (watercolor paint).

[0021] The above components were mixed by heating with stirring, and the mixture was poured and cooled to solidify to obtain a solid drawing material (crayon).

[0022] The above components were mixed by heating with stirring, and the mixture was poured and solidified by cooling to obtain a solid drawing material (pass).

Comparative Example 1 PEARL-GLAZE MB-2100R of Example 1
The same MF-100 (titanium oxide coverage 38%, particle size 5
A water-soluble drawing material (watercolor paint) was obtained in the same manner as in Example 1 except that the thickness was changed to 30 μm).

Comparative Example 2 PEARL-GLAZE MG-2100R of Example 3
ME-100 (titanium oxide coverage 29%, particle size 10
A water-soluble drawing material (watercolor paint) was obtained in the same manner as in Example 1 except that the water content was changed to 60 μm).

Comparative Example 3 PEARL-GLAZE MY-2100R of Example 5
The same MRY-100 (titanium oxide coverage 38%, particle size 1
0 to 60 μm) in the same manner as in Example 1, except that
A solid drawing material (pass) was obtained.

Using the water-soluble drawing material and the discoloring gloss drawing material of the solid drawing material obtained in Examples 1 to 5 and Comparative Examples 1 to 3, the color of the applied drawing trace was 60 to 80 ° in visual angle and 10
Confirmed at ~ 30 °. The results are shown in Table 1.

[0027]

[Table 1]

Drawing method of water-soluble drawing material: The water-soluble drawing material of the discoloring gloss drawing material obtained in the above example and water were mixed at a weight ratio of 4: 1 and the drawing brush (No. 6 writing brush, Pentel ( Co., Ltd.) is applied in the left-right direction and the up-down direction, and is repeatedly applied so that the application surface is uniform. Drawing method of solid drawing material: After leaving the solid drawing material of the discoloring gloss drawing material obtained in the above example at room temperature for 1 day, the application pressure of 300 g ±
It is repeatedly coated at 100 g in a section of 5 cm in length and 5 cm in width so that the coating surface is uniform in the left-right direction and the vertical direction.

[0029]

As described above in detail, the color-changing, glossy drawing material according to the present invention is an excellent drawing material in which the color of the drawing mark changes depending on the viewing angle.

Claims (6)

[Claims] 1. The coverage of titanium oxide is 42% or more and 68% or more.
A discoloring luster drawing material comprising at least the following pearl pigment and a fixing agent. 2. The discolorable gloss drawing material according to claim 1, wherein the fixing agent is a water-soluble resin or a resin emulsion, and further contains water. 3. The discolorable gloss drawing material according to claim 2, further comprising a water-soluble high-boiling point solvent. 4. The discoloring gloss drawing material according to claim 1, wherein the fixing agent is a wax. 5. The particle diameter of the pearl pigment is 5 μm or more 6
The discolorable gloss drawing material according to any one of claims 1 to 4, which has a thickness of 0 µm or less. 6. The discoloring gloss drawing according to claim 1, wherein the pearl pigment is contained in an amount of 20% by weight or more and 40% by weight or less based on the total amount of the discoloration glossing drawing material. Material.