JP2003253187A - Visual angle-dependent multicolor composition, ink composition for writing utensil, and writing utensil - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a visual angle-dependent multicolor composition which has visual angle-dependent multicolor properties exhibiting a desired color change different from the color change inherent in visual angle-dependent multicolor particles. <P>SOLUTION: This visual angle-dependent multicolor composition contains visual angle-dependent particles and a pearl 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 a viewing-angle-dependent polychromatic composition for inks, resin-forming products, paints, paints, cosmetics and stamps having a desired viewing-angle-dependent polychromaticity of color change.

[0002]

2. Description of the Related Art Pigments and dyes having a color tone of white, red, yellow, etc. are widely used as colorants contained in a composition as a decorative effect. In addition, an ink composition using a metallic color such as gold or silver for visual effects, or a metal pigment or a pearl pigment for obtaining a pearly handwriting is provided. Examples of such an ink composition include, for example, JP-A-7-
No. 118592 and JP-A-8-151547 disclose an aqueous ink composition using an aluminum pigment and an aqueous ink composition using a pearl pigment.

In addition to the above pigments, the ink composition has a different effect from metal powder pigments and pearl pigments. Ink compositions containing viewing angle dependent pleochroic particles have been used to obtain coatings.

[0004]

However, the visual angle-dependent polychromatic composition capable of obtaining a handwriting or coating film having the visual angle-dependent polychromaticity is a visual-angle-dependent polychromatic particle contained in the ink composition. Has a fixed discoloration property depending on the viewing angle, for example, when using viewing angle-dependent polychromatic particles that change color from red to yellow (gold), when a blue or green colorant is added, a white background Although there was a change in hue, it was not possible to change the hue on a black background. The hue on the black background could not be changed for other viewing angle-dependent polychromatic particles. Further, even on a white paper, when a dye or an organic pigment is used, these colorants ooze out on the paper surface, and it is difficult to obtain a uniform handwriting. Therefore, even if a normal colorant is added, the change in color due to the viewing angle is fixed to the color change of the viewing angle dependent polychromatic particles, and a composition giving a handwriting or a coating film having a desired color change has been obtained. Absent.

[0005]

Therefore, the present inventors have
As a result of diligent studies, the use of the viewing-angle-dependent polychromatic composition, which is a composition containing the viewing-angle-dependent polychromatic particles and the pearl pigment, results in the color change exhibited by the viewing-angle-dependent polychromatic particles alone. The present inventors have found that it is possible to obtain a handwriting or a coating film that exhibits a color change different from

[0006]

DETAILED DESCRIPTION OF THE INVENTION The present invention is a viewing angle dependent pleochroic composition comprising viewing angle dependent pleochroic particles and a pearl pigment. By including the viewing angle-dependent polychromatic particles and the pearl pigment in the composition, a color change different from the original color change exhibited by the viewing angle-dependent polychromatic particles occurs, and the desired hue change depending on the viewing angle on the handwriting or the coating film. Can be realized. The viewing-angle-dependent polychromatic composition of the present invention has a visual effect, and thus is particularly suitable as an ink composition for writing instruments or stamps.

(Viewing Angle Dependent Polychromatic Particles) The viewing angle dependent polychromatic particles exhibit the effect of appearing in different colors depending on the viewing angle, such as viewing angle dependent polychromatic particles and dichroic pigments. It is defined as a general term for pigment particles whose color tone (interference color) changes depending on the viewing angle. The viewing angle-dependent polychromatic particles are not particularly limited as long as they are such particles. For example, laminated pigments such as minerals, metals, metal compounds, and metal oxides, liquid crystal polymers, and deposited layers of liquid crystal polymers are included. These view-angle-dependent multicolored laminated particles exhibit a view-angle-dependent polychromatic effect by an interference color generated by light interference, and include so-called iris color pigments.

As the viewing angle dependent polychromatic particles of the present invention, particles having a laminated structure and having an optical reflection layer are preferably used.
The multilayer structure has a substrate layer and a coating layer, the coating layer may be a single layer or a multilayer, and the optical reflection layer may be an inner layer or an outer layer of particles. Further, the optically reflective layer may be a substrate layer or a coating layer of particles. In addition, the optically reflective layer also includes a case where the optically reflective layer is formed as a substance independent of the above particles as an optical reflector. Further, for example, the optical reflection layer has a reflectance of 0.3 or more, or 0.4 or more, or preferably 0.
Particles having a size of 5 or more are preferably used.

A preferred combination of the substrate layer and the coating layer of the viewing angle dependent polychromatic particles of the present invention is, for example, particles composed of silicon oxide as the substrate layer and iron oxide or titanium oxide as the coating layer, for example, Product name "Color St
"Ream Autumn Mystery", "Colo
r Stream T20-01 W2 "," Color
Stream F20-00 W2 "(manufactured by MERCK).

As a preferred combination of the substrate layer and the coating layer of the viewing angle dependent polychromatic particles, the substrate layer is made of an aluminum film, and the coating layer is a magnesium fluoride film on the substrate layer side and an anti-substrate layer. It is preferable to form the chrome film on the side. For example, "Roger W. Ph
illips et al. USP 5,65379
2 (1997), Flex Products, IN
C. And aluminum coated with magnesium fluoride or chromium can be used. For example Flex
Products, INC. Product name "CHRO"
MAFLAIR ”can be illustrated.

As the viewing angle-dependent polychromatic particles, flaky smooth viewing angle-dependent polychromatic particles having an optical specular reflection layer can be preferably used. For example, it is composed of smooth flake-shaped laminated particles consisting of a substrate layer having an optical specular reflection surface and a coating layer that interferes with light, and the substrate layer is composed of a specular reflection metal film. The layer is a particle composed of a metal or metal compound film having different refractive indexes. In the case of this particle, the light incident on the surface of the particle is partially reflected on the surface of the coating layer and partially refracted, reflected, and transmitted inside the coating layer, and the light of the partially refracted and transmitted wavelength Is then reflected by the substrate layer and then refracted and transmitted again by the coating layer, and when this light interferes with the light reflected on the surface and inside of the coating layer as light of a specific wavelength, from within the particle, As an interference light of a specific wavelength emitted to the outside of the particle, an interference color according to the viewing angle is given. The substrate layer of the metal coating film is not particularly limited, but a simple metal or an alloy having a light reflectance of 0.5 or more is preferable. Specifically, silver (reflectance: 0.94), aluminum (reflectance: 0.83), gold (reflectance: 0.8)
0), nickel (reflectance: 0.63) and the like.

Further, the substrate layer is not limited to the metal film, and iron oxide Fe ₂ O ₃ can also be used. The coating layer is also not particularly limited, and a semi-transparent metal or metal compound (including metal oxide) having a hard refractive index and a transparent metal or metal oxide (including metal oxide) having a low refractive index are alternately used. A laminated product can be used.

The substrate layer is iron oxide Fe ₂ O ₃ ,
The surrounding area is composed of silicon oxide SiO ₂ and iron oxide Fe ₂ O ₃ 2
A layer coated with a metal film can be preferably used. As an example, as a pigment particle in which aluminum or MIO (mica-like iron oxide) is laminated as a substrate layer and silicon oxide and iron oxide are laminated in this order as a coating layer, for example, a product name “Variocrom Magic Red L4” manufactured by BASF Corporation is used.
420 "," Variocrom Magic Purp "
le L5520 ”or“ Variocrom M
"Agic Gold L1400" can be illustrated. Further, particles made of aluminum-manganese as the coating layer and particles of mica-like iron (III) oxide as the substrate layer can be used. For example, the product name “Pal manufactured by BASF Ltd.
iocrom Copper L3000 "and" Pal
iochrom Copper L3001 ”can be exemplified.

As described above, the viewing angle dependent polychromatic particles include a substrate layer and a coating layer in the particles, and the substrate layer or the coating layer is at least a silicon compound, an iron compound, an aluminum compound, and a titanium oxide. It is preferable that the viewing angle-dependent pleochroic particles include any one of the compounds.

Cholesteric liquid crystal polymers can also be preferably used as the viewing angle-dependent polychromatic particles.
The term “cholesteric liquid crystal polymer” as used in the present invention is a glittering material defined as particles of a cholesteric liquid crystal polymer having a helical structure, and is flaky particles.
For example, a layer of liquid crystal polymer particles that are optically aligned in one direction are laminated to form an optically reflective layer by laminating a plurality of layers so that the orientation direction of the polymer particles is in a hierarchical spiral shape. Particles can be used. As a result, the cholesteric liquid crystal polymer particles show that due to the helical overlap of the optically oriented polymer particles, depending on the viewing angle, some wavelengths of the light incident on the particle surface in a wide spectral range are It has the property of reflecting only the spectral components in the region and transmitting all wavelengths in other regions. The region of the reflected spectral component is determined by the pitch width of the optical reflection layer when the orientation of the polymer particles makes one rotation (one cycle), and the refractive index of the material.
The reflected spectral region is split into light components polarized into a left spiral and a right spiral, where one is reflected and the other is transmitted, depending on the direction of rotation of the helix, so that this cholesteric liquid crystal polymer is It is transparent over a wide spectral range. By using this liquid crystal polymer, it is possible to obtain a handwriting or a coating film having viewing angle-dependent polychromaticity, which is the object of the present invention. In addition, the cholesteric liquid crystal polymer particles are excellent in dispersibility because of their low specific gravity as compared with the conventional aluminum pigments, pearl pigments, the viewing angle dependent polychromatic particles and the like. Furthermore, even at low viscosity, the cholesteric liquid crystal polymer particles have little sedimentation. Also,
Since the cholesteric liquid crystal polymer particles have high transparency, a new color effect can be obtained without clouding of colors by mixing two or more kinds of cholesteric liquid crystal polymer particles. Further, it is possible to change the color tone by blending the color of the base and another colorant. Examples of the cholesteric liquid crystal polymer particles used in the present invention include "HELICONE 450" and "D5" manufactured by Wacker-Chemie GmbH of Germany.
16 ”,“ same 575 ”,“ same 624 ”, and“ same HC ”.

As the viewing angle-dependent polychromatic particles used in the present invention, the various particles exemplified above can be used alone, but two or more kinds of particles can be used in combination.

The median diameter of the viewing angle-dependent polychromatic particles used in the present invention is preferably 1.0 to 100 μm when the viewing angle-dependent polychromatic composition of the present invention is used as an ink composition. The median diameter of flake pigment is 1.0 μm
When it is less than 200 μm, the color development is poor because the particles are too small, and when it exceeds 200 μm, when it is used as an ink for writing instruments or applicators such as ballpoint pens, which require the particles to pass through a narrow tube, the ink will come out It is not preferable because it is difficult. Further, in order to obtain an ink that achieves better color development and is suitably used for a writing tool or applicator such as a ballpoint pen that needs to pass through a narrow tube, the maximum diameter of the particles is 1.0 to 200 μm, Is preferably 10 to 100 μm.

When the viewing angle-dependent polychromatic composition of the present invention is used as a stamp ink, it is preferable that the viewing angle-dependent polychromatic particles have an average particle size of 500.0 μm or less. The average particle size of viewing angle dependent polychromatic particles is 500.0μ
When it exceeds m, when it is used as a stamp ink in which particles need to pass through the narrow holes of the sponge, it is difficult to come out of the sponge, which is not preferable. The average particle size of the viewing angle-dependent polychromatic particles that is more suitable as the stamp ink is 1.0 to
It is 110.0 μm.

When the viewing angle-dependent polychromatic composition of the present invention is used as an ink composition, the viewing angle-dependent polychromatic particles used in the viewing angle-dependent polychromatic composition of the present invention are 0 in the total amount of the ink composition. It is preferably contained in an amount of 0.5 to 40% by weight.
The visual angle-dependent multicolor particles are 0.5 in the total amount of the ink composition.
When the content is less than wt%, the color developability on a white background and the viewing angle-dependent polychromaticity are not sufficient. Further, when the viewing angle-dependent multicolor particles exceed 40% by weight in the total amount of the ink composition, the solid content increases, the fluidity of the ink decreases, and the writability deteriorates. The optimum blending amount of the viewing angle-dependent polychromatic particles is 1.0 to 20.0% by weight based on the total amount of the ink composition.

The viewing angle-dependent polychromatic particles used in the present invention are
It is preferably in the form of flakes (plates). By using flake-shaped particles, the writing surface or the coating surface is easily covered, and the visual angle-dependent polychromatic interference color appears strongly, and the visual angle-dependent polychromatic interference color is evenly distributed on the writing surface or the coating surface. Can be given.

(Pearl Pigment) The pearl pigment of the present invention is not particularly limited as long as it has a pearly luster, and mica (mica) is coated with a metal oxide such as titanium dioxide or iron oxide. It may be a mica pigment or a pigment in which mica-shaped iron oxide (MIO) is coated with a metal oxide such as titanium oxide. Examples of pearl pigments include trade names “Iriodin 7205”, “Iriodin 7215”, and “Iridin 7205”.
odin 7217 ”,“ Iriodin 7219 ”,“ Iriodin
7225 ”,“ Iriodin 7235 ”,“ Iriodin 20
5 "," Iriodin 215 "," Iriodin 217 "," Irio
"din219", "Iriodin225", "Iriodin235"
(Above, manufactured by Merck) can be used. The pearl pigments can be used alone or in combination of two or more kinds.

When the viewing angle-dependent pleochroic composition of the present invention is used as an ink composition, the pearl pigment used in the present invention is preferably contained in an amount of 0.5 to 40% by weight based on the total amount of the ink composition. . When the amount of the pearl pigment is less than 0.5% by weight in the total amount of the ink composition, the original hue change of the view-angle-dependent multicolor particles used in the view-angle-dependent multicolor composition of the handwriting or the coating film is desired. It is difficult to obtain a hue change. On the other hand, if the pearl pigment exceeds 40% by weight in the total amount of the ink composition, the solid content increases, the fluidity decreases, and the writability decreases. The optimum blending amount of the pearl pigment is 1.0 to 20.0% by weight in the total amount of the ink composition.

The particle size of the pearl pigment used in the present invention is not particularly limited, but when the viewing angle-dependent pleochroic composition of the present invention is used as an ink composition, the average particle size is 1 to 10.
It is preferably 0 μm. When the average particle diameter of the pearl pigment is less than 1 μm, it is necessary to add a large amount of pearl pigment to obtain a desired color change. Further, when the average particle diameter of the pearl pigment is larger than 100 μm, the pen tip is likely to be clogged.

The view-angle-dependent polychromatic composition of the present invention contains at least view-angle-dependent polychromatic particles and a pearl pigment. By including the pearl pigment, the hue change of the view-angle-dependent polychromatic composition depends on the view angle. It is not fixed to the color change of the polychromatic particles, and various color changes can be realized depending on the type of pearl pigment. For example, viewing angle dependent polychromatic particles that change color from red to yellow (trade name “Color Stream
When a blue-based pearl pigment (trade name "Iriodin 7225", manufactured by Merck & Co., Inc.) is added to a viewing angle-dependent pleochroic composition containing "Autumn Mystery", manufactured by Merck & Co., Inc. can do. Similarly, viewing angle-dependent polychromatic particles (trade name "Color Stream Au
in a viewing angle dependent pleochroic composition containing "TumnMystery" manufactured by Merck & Co., Inc.
iodin7219 ", manufactured by Merck & Co., Inc.) changes hue from pink to silver when mixed with green pearl pigment (trade name" Iriodin 7235 ", manufactured by Merck & Co.), changes from brown to green hue, yellowish A hue change from gold to orange when a pearl pigment (trade name "Iriodin 7205", manufactured by Merck) is mixed, and a gold color when a red pearl pigment (trade name "Iriodin 7215", manufactured by Merck) is mixed. To red hue change, orange pearl pigment (trade name "Iriodin7
217 ", manufactured by Merck & Co., Inc.) can change the hue from gold to red, and by appropriately selecting a pearl pigment, a desired color depending on the viewing angle of the viewing angle-dependent polychromatic composition can be obtained. You can get a change. In the glitter composition of the present invention, the ratio of (1) viewing angle dependent polychromatic particles to (2) pearl pigment is not particularly limited, but (1) / (2) = 90 / 10-10 /
It is preferably 90 (mass ratio). The ratio is 90 /
If it exceeds 10, it is difficult to obtain a color change different from the original color change of the viewing angle-dependent polychromatic particles (if there are too many viewing angle-dependent polychromatic particles). If there are too few particles) it is difficult to obtain viewing angle dependent pleochroism in the composition or handwriting or coating.

(Dark colorant) When the visual angle-dependent polychromatic composition of the present invention is used for forming a handwriting or a coating film by applying it to an object to be coated, such as an ink composition, etc. In order to obtain a desired hue change depending on the viewing angle even when a handwriting or a coating film is formed on a white coated object such as white paper, the viewing angle dependent polychromatic ink composition contains a dark colorant. Is preferred. The viewing angle-dependent polychromatic composition of the present invention changes color even when it does not contain a dark colorant, but on a white paper, to make the handwriting easier to see and to make it easier to confirm the color change. In addition, it is preferable to include a dark colorant. The dark colorant is not particularly limited as long as it has a property of penetrating the surface of the paper and forming a base for coloring the pearl pigment, and includes a black dye, a black pigment, a blue dye, a blue pigment, and green. Although a dye, a green pigment, a purple dye, a purple pigment, a colored aluminum flake, a colored resin sphere or the like can be used, it is preferable to use a black colorant such as a black dye or a black pigment in the viewing angle-dependent polychromatic composition of the present invention. This is preferable because a uniform handwriting can be obtained when the product is an ink composition. As the black dye, for example, a trade name “Water
Black R500 "(manufactured by Orient Chemical Co., Ltd.), a trade name" Fastgen Super Violet RVS "(manufactured by Dainippon Ink and Chemicals, Inc.) as a purple pigment, and a trade name" Acid Violet 4BL "as a purple dye.
(Sumitomo Chemical Co., Ltd.) can be used, and as the black pigment, for example, a product name “Monarch 800” (manufactured by Cabot Corporation) and a product name “PRINTEX G” (manufactured by Degussa) can be used. The dark colorants of the present invention are black, dark, very dark, dark gray and dark with a lightness of 4 or less, which is defined in "Object Color Name" of JIS Z 8102 (1985). The coloring agent to be exhibited is preferable because a desired hue change depending on a viewing angle can be satisfactorily obtained even when a handwriting or a coating film is formed on a white object to be coated.

In order to darken the base of the viewing angle-dependent multicolor particles, it is preferable that the pigment which is a dark color pigment has a particle size sufficiently smaller than the thickness of the viewing angle-dependent multicolor particles. . This particle size is measured by a centrifugal sedimentation type light transmission type particle size distribution meter (for example, CAPA-700 manufactured by Horiba Ltd.),
The average particle size is preferably 0.01 to 0.5 μm. It is impossible to measure with a pre-measuring machine, but when the average particle size of the pigment is less than 0.01 μm, the transparency of the pigment theoretically increases, and the dark color of the base of the viewing angle dependent polychromatic particles For chemical use, there is a problem that a large amount of pigment needs to be added. When the maximum diameter of the flake-shaped viewing angle-dependent multicolored particles is less than 10 μm, the thickness of the viewing angle-dependent multicolored particles as a handwriting or a coating film is about 0.5 μm. Therefore,
Pigment particles having an average particle size of more than 0.5 μm hinder the reflection of light on the surface of the viewing-angle-dependent polychromatic particles, or hide the surfaces of the viewing-angle-dependent polychromatic particles so that the desired effect of the viewing-angle-dependent polychromaticity is obtained. It becomes impossible to observe enough. The optimum average particle size of the pigment (optical absorbent) measured by the above particle size distribution meter is 0.03.
Is about 0.3 μm.

The content of the dark colorant in the viewing angle-dependent polychromatic composition is 0.01 to the total amount of the viewing angle-dependent polychromatic composition.
It is preferable to contain 20% by weight, and 0.05 to 5% by weight
Is more preferable. When the content is less than 0.01% by weight in the total amount of the viewing angle-dependent multicolored composition, when the viewing angle-dependent multicolored composition of the present invention is applied on a white article such as a white paper, The color development of the pearl pigment is hindered by the light reflection of the white coating material, and the color change depending on the viewing angle of the handwriting or the coating film by the viewing angle-dependent polychromatic composition becomes the original color change of the viewing angle-dependent polychromatic particles. . When the content is more than 20% by weight, the concentration of the colorant due to the dark colorant is high, so that the color of the dark colorant causes the visual angle-dependent multicolor particles or the pearl pigment to be colored. Be hindered.

(Polysaccharide) The viewing angle-dependent pleochroic composition of the present invention may contain a polysaccharide when used as an aqueous ink composition. The polysaccharide is not particularly limited as long as it can prevent the precipitation of the viewing-angle-dependent polychromatic particles and the pearl pigment and can adjust the viscosity, but a microbial polysaccharide and its Derivatives, water-soluble plant-based polysaccharides and their derivatives, and water-soluble animal-based polysaccharides and their derivatives can be used. The polysaccharide may be dissolved in water to form an aqueous solution and used as a viscosity modifier.

As the above-mentioned polysaccharide, for example, a microbial-derived polysaccharide and its derivative are used. Examples thereof include pullulan, xanthan gum, welan gum, rhamsan gum, succinoglucan, dextran and the like. In addition, water-soluble plant polysaccharides and their derivatives are used. For example, tragacanth gum, guar gum, tara gum, locust bean gum, gum arabic, pectin,
Examples thereof include starch, carrageenan, agar, alginic acid and the like. In addition, water-soluble animal polysaccharides and their derivatives are used. For example, gelatin and casein can be exemplified. These polysaccharides are substances having the property of being decomposed into monosaccharides such as glucose and mannose, which are the constituent units of the polysaccharide, when subjected to a predetermined decomposition treatment.

When water is used in the present invention, among the above-mentioned saccharides, microbial polysaccharides and their derivatives are used. In particular, zansan gum, welan gum, rhamsan gum, succinoglucan, microbial-derived polysaccharides and derivatives thereof selected from dextran, the viewing angle-dependent polychromatic particles laminated particles containing a plurality of metal elements, the cholesteric large particle size. Even liquid crystal polymers have excellent pseudoplastic flow characteristics, have a good effect of preventing the settling of viewing-angle-dependent polychromatic particles over a long period of time, and have excellent storage stability as an ink. Above all, the pseudoplastic flow characteristics for flaky smooth viewing angle dependent polychromatic particles are excellent.
Therefore, when applied to a writing instrument such as a pole pen, the above-mentioned particles flow out uniformly and satisfactorily from the tip of the tip during writing, and smooth flaky viewing-angle-dependent polychromatic particles are aligned horizontally on the handwriting or coating film. It is easy to see strong interference light (interference color) in the handwriting or coating film. The above-mentioned polysaccharides can be used alone or in combination of two or more.

The content of the polysaccharide in the viewing angle-dependent polychromatic composition is preferably 0.01 to 20% by weight, preferably 0.05 to 5% by weight, based on the total amount of the viewing angle-dependent polychromatic composition. %
More preferably, it is included. When the amount of the polysaccharide exceeds 20% by weight based on the total amount of the viewing angle-dependent pleochroic composition, the viscosity of the ink becomes high and the writability deteriorates. When the amount of the saccharide is less than 0.01% by weight based on the total amount of the viewing angle-dependent polychromatic composition, the effect of preventing the precipitation of the viewing angle-dependent polychromatic particles and the pearl pigment is insufficient, and the pen tip tends to be clogged.

(Other Components) The visual angle-dependent polychromatic composition of the present invention comprises, as other components, a solvent such as a water-soluble organic solvent, a surfactant, a lubricant, an antiseptic, a fungicide, and a dark color system. Other colorants (organic pigments, dyes) and resin components may be included. Further, the above-mentioned components and other well-known components may be contained in order to adapt them to applications such as resin-formed products, paints and cosmetics.

In the present invention, a solvent can be used. Depending on the purpose, the solvent can be selected from a case where water is the main solvent and a case where the organic solvent is the main solvent and does not substantially contain water.
When water is used as a main solvent, it is used for the purpose of imparting a slow drying property to the ink composition and preventing the pen tip or the like containing the ink from drying. In the water-based ink composition, a water-soluble organic solvent can be added in order to further delay the drying speed of water in order to prevent the nib and the like from drying. For example, glycols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol and polyethylene glycol, polyhydric alcohols such as glycerin, ethylene glycol monomethyl ether, diethylene glycol. Examples thereof include glycol ethers such as rumonomethyl ether, dipropylene glycol monomethyl ether, and dipropylene glycol monopropyl ether. These organic solvents may be used alone or in combination of two or more.

When an organic solvent is used as the main solvent, it can be applied to both the purpose of making the ink quick-drying and the purpose of making it difficult to volatilize. By gelling, it is easy to obtain a rod-shaped solid ink. The choice of organic solvent is
One kind or two or more kinds of organic solvents can be appropriately used according to the characteristics required for the ink such as quick drying and slow drying. Examples of organic solvents include toluene, aromatic hydrocarbons such as xylene, alicyclic hydrocarbons such as methylcyclohexane and aliphatic hydrocarbons, alcohols such as ethyl alcohol, isopropyl alcohol, benzyl alcohol, methyl ethyl ketone, methyl. Examples include ketones such as isobutyl ketone and isophorone, esters such as ethyl acetate and butyl acetate, ether alcohols such as cellosolve, butyl cellosolve, and propylene glycol monomethyl ether.

In addition, in the present invention, if necessary, as the surfactant, a nonionic, anionic, cationic, betaine-based, silicon-based, fluorine-based surfactant or polyoxyethylene alkali is appropriately used. Lubricants such as metal salts, dicarboxylic acid amides, phosphoric acid esters, N-oleyl sarcosine salts, rust inhibitors such as benzotriazole and tolyltriazole dicyclohexylammonium nitrate, benzoisothiazoline type, pentact and phenol type, antiseptic agents such as cresol Molds and the like can be included in the viewing angle dependent pleochroic composition. These additives are 1
One kind or two or more kinds can be used.

In the present invention, a colorant (organic pigment, dye) having a hue (white, red, etc.) other than a dark color system is added to the visual angle-dependent polychromatic composition to develop the visual angle-dependent polychromatic particles and the pearl pigment. Can be included to the extent that it is not alienated. For example, an inorganic pigment (for example, titanium oxide or the like), an organic pigment (for example, an azo pigment, a condensed polyazo pigment or the like), a resin coloring body, a dye or the like can be used. The colorants may be used alone or in combination of two or more.

In the present invention, or viewing angle dependent pleochroic particles,
In particular, a resin component can be used for the purpose of fixing the flake-shaped viewing angle-dependent polychromatic particles to a substance to be coated (base), forming a coating film for protecting the substance to be coated, and forming a resin-formed product. . The resin component used in the present invention can be appropriately selected and used from the components of the resin miscible with the solvent. A water-soluble sizing agent is preferably used as the resin component when water is used as the solvent. For example, gum arabic, dextrin derivative, cellulose derivative such as carboxymethyl cellulose, polyvinyl alcohol, polyvinylpyrrolidone, polyacrylic acid, acrylic acid-based copolymer, and other water-soluble functional groups such as maleic anhydride. Water-soluble natural or synthetic resins, such as monomers, can be preferably used. In addition, unlike the above resins, an emulsion or a dispersion type sizing agent, which is not dissolved in water but can be mixed in a dispersed state, can be preferably used for the purpose of fixing the flake pigment to the base.

An oil-soluble resin is preferably used as a resin component when an organic solvent is used as the solvent. As an example, aliphatic, alicyclic, aromatic petroleum hydrocarbon resin, styrene-based, acrylic ester-based, vinyl acetate-based, vinyl resins such as terpene-based, polyvinyl acetal resin such as polyvinyl butyral, phenol-based, Formalin condensation resins such as xylene-based, acrylic ester-based, vinyl acetate-based, and terpene-based resins and their alkyl-modified resins, as well as synthetic resins, semi-synthetic and natural oil-soluble resins such as polyamide resins, ketone resins, rosin or its modified resins. Can be appropriately selected and used depending on the type of organic solvent.

When the viewing angle-dependent pleochroic composition of the present invention is used in an ink composition, the resin component is contained in an amount of 1.0 to 30.0% by weight based on the total amount of the ink composition. It is preferable. If the amount of the above resin component is less than 1.0% by weight based on the total amount of the ink composition, the fixability of the viewing angle-dependent multicolored particles onto the base is insufficient, and the amount based on the total amount of the ink composition is 30.0%.
When the content is more than wt%, the viscosity of the ink is too high, the fluidity is lowered, and the writability is lowered. The optimum blending amount of the resin component is 5.0 to 20.0% by weight. Moreover, the above-mentioned resin components can be used alone or in combination of two or more.

(Viscosity range) When the viewing angle-dependent polychromatic composition of the present invention is used as an ink composition, the preferred viscosity range of the ink composition is 500 to 15000 mPa · s. The viscosity is a value measured by an ELD viscometer (3 ° R14 cone, rotation speed: 0.5 rpm, 20 ° C).

(Usage form) As a usage form of the present invention,
Although not particularly limited, examples of preferred usage forms include a view angle-dependent polychromatic composition stored in a bottle-shaped container such as nail enamel, and a form of applying with a brush, metal or resin, etc. A configuration in which a viewing angle-dependent polychromatic composition is housed in a tube, and only a necessary amount is squeezed from the tube to be used, and an ink storage material such as a sponge in a cylindrical container is impregnated with the viewing angle-dependent polychromatic composition Directly stamp with the form of applying the viewing angle dependent polychromatic composition, the viewing angle dependent polychromatic composition is housed in the ink containing tube, and the application part such as a ballpoint pen tip is arranged at one end of the ink containing tube The form in which the ink is applied with is mentioned. Further, a mode in which the viewing angle-dependent multicolored composition of the present invention is diluted to a desired viscosity as a liquid, and then the viewing angle-dependent multicolored composition is applied by brush or spray,
The visual angle-dependent polychromatic composition may be injected into the mold and then solidified to form a resin molded product.

A particularly preferred form is a so-called water-based gel ink ballpoint pen. The inventor or the applicant has also filed an invention relating to the form of a writing instrument suitable for using flake pigment particles and a ballpoint pen tip (Japanese Patent Application Nos. 11-258189 and 265232,
No. 265233, Japanese Patent Application No. 2000-30124). These adoptions are optimal for obtaining handwriting with the ballpoint pen of the ink composition of the present invention.

The method for producing the viewing angle-dependent polychromatic composition used in the ball-point pen of the present invention can be produced by a general production method and is not particularly limited. When using a pigment in the dark colorant used in the present invention,
A pigment, which is a dark colorant, may be dispersed before the production of the viewing angle-dependent multicolored composition and used as a pigment dispersion in the production of the viewing angle-dependent multicolored composition. Further, the polysaccharide used in the present invention may be dissolved in water as a viscosity modifier before the production of the viewing angle-dependent polychromatic composition, and may be used in the production of the viewing angle-dependent polychromatic composition. . In the above production, conventionally known dispersion methods, defoaming methods, filtration methods and the like can be adopted.

[0044]

EXAMPLES Examples and comparative examples of the present invention will be described below.

(Example of Preparation of Pigment Dispersion) With the composition and formulation shown in Table 1, a black pigment dispersion and a green pigment dispersion were prepared by the following operations. First, a styrene acrylic resin is heated and dissolved together with sodium hydroxide and ion-exchanged water using a known stirring device, ethylene glycol and a black pigment or a green pigment are added and stirred, and then the dispersion of Table 1 is performed using a known bead mill. By dispersing over time, a black pigment dispersion and a green pigment dispersion having a pigment concentration of 10% by weight were obtained. The product name "Monarch 800" is used for the black pigment.
(Manufactured by Cabot), trade name "Fastgen Green B" (manufactured by Dainippon Ink and Chemicals, Inc.) as a green pigment, and product name "John Krill 683" for styrene acrylic resin.
(Manufactured by Johnson Polymer Co., Ltd.) was used, and reagents were used for sodium hydroxide and ethylene glycol.

[0046]

[Table 1]

(Example of Preparation of Viscosity Modifier) Succinoglycan (trade name "Reozan", manufactured by Sansei Co., Ltd.), which is a polysaccharide, was added to ion-exchanged water so that the concentration of the polysaccharide would be 1% by weight, The mixture was stirred for 1 hour with a known stirring device to obtain a 1% by weight aqueous solution of succinoglycan, which was used as a viscosity modifier.

(Examples and Comparative Examples) The raw materials having the blending amounts shown in Tables 2 and 3 were put into a known stirrer, and the mixture was stirred by stirring for 1 hour, filtered, and then defoamed. The aqueous ink compositions of Examples 1 to 8 and Comparative Examples 1 to 6 were obtained. Conventionally known methods were used for the dispersing method, the defoaming method, the filtering method, and the like. The blending amounts in Tables 2 and 3 are% by weight.

[0049]

[Table 2]

[0050]

[Table 3]

The following materials were used as the raw materials in Tables 2 and 3. (Viewing angle-dependent polychromatic particles) A: Trade name "Color Stream Autumn"
"myatery", manufactured by Merck & Co., Inc. B: trade name "Variocrom Magic Re"
d "(BASF) C: Trade name" Helicorn Jade "
(Chemie) (Pearl pigment) A: Product name "Iriodin 7235", manufactured by Merck B: Product name "Iriodin 7225", manufactured by Merck C: Product name "Iriodin 7219", manufactured by Merck (dark colorant) Black dye: Product name "Water Black R50
0 ", blue dye manufactured by Orient Chemical Co., Ltd .: trade name" Water Blue # 11 "
6 ", black pigment dispersion manufactured by Orient Chemical Co., Ltd .: The black pigment dispersion of the above Preparation Example was used. Green pigment dispersion: The green pigment dispersion of the above preparation example was used. (Water-soluble organic solvent) Glycerin: Reagent (polysaccharide) Viscosity modifier: The viscosity modifier of the above-mentioned preparation example was used.

(Evaluation) Each of the aqueous ink compositions of Examples 1 to 8 and Comparative Examples 1 to 6 was semi-continuous with a ball-point pen tip made of stainless steel (ball material: silicon carbide, ball diameter: 1.0 mm) connected at one end. A ball-point pen of each test sample was prepared by filling an ink containing section made of a transparent polypropylene hollow shaft cylinder and loading the ink containing section. For each test sample, the color change with angle on white paper, the color change with angle on black paper, and the uniformity of handwriting were evaluated. The results are shown in Table 2.

(Color Change Depending on Angle on White Paper) Each test sample was written on Kent paper to prepare a handwriting sample, and the color change was evaluated by visually observing while changing the angle of the paper surface.

(Color Change According to Angle on Black Paper) Each test sample was written on a black drawing paper to prepare a handwriting sample, and visually observed while changing the angle of the paper surface to evaluate the color change. .

(Uniformity of Handwriting) Each test sample was written on Kent paper to prepare a handwriting sample, which was visually evaluated according to the following criteria. Uniform: Uniform handwriting was obtained and a clear color change was observed. Non-uniformity: Since the colorant that is the base is bleeding, handwriting in the form of an edge is formed, and no clear color change is observed.

(Results) The color change of the viewing angle-dependent polychromatic ink composition of Example 1 was a change from yellow green to pink in both the angle change on white paper and the angle change on black paper. It was On the other hand, the color change of the ink composition of Comparative Example 1, which is the ink composition containing the viewing angle-dependent polychromatic particles A used in Example 1 and not containing the pearl pigment, is the change of the color on the white paper depending on the angle. Was a change from orange to yellow, and the color change with angle on black paper was a change from red to yellow. A viewing angle dependent polychromatic ink composition containing a viewing angle dependent polychromatic ink composition and a pearl pigment, which does not contain a dark colorant, has a color change depending on the angle on a white paper and a color change depending on the angle on a black paper. In both cases, a color change different from the original color change of the viewing angle-dependent polychromatic particles A was observed in the handwriting.

Example 2 and Example 3 are viewing angle dependent polychromatic ink compositions containing viewing angle dependent polychromatic particles A and pearl pigment A, and further containing a black dye or a black pigment as a black colorant, respectively. is there. In Example 2 and Example 3, the handwriting was a color change from brown to green in both the color change depending on the angle on the white paper and the color change depending on the angle on the black paper.
On the other hand, in Comparative Example 2 which is an ink composition containing no pearl pigment, the color change depending on the angle on the black paper is red to yellow, and the color change depending on the angle on the white paper is red to yellow, Compared to Comparative Example 1, the color change was the same as or close to the original color change of the viewing angle-dependent polychromatic particles A.

Examples 7 and 8 are viewing angle-dependent polychromatic ink compositions containing viewing angle-dependent polychromatic particles A and pearl pigment A, each containing a green pigment or a blue dye as a dark colorant. is there. In Example 7, the handwriting was a color change from yellow-green to brown in both the color change depending on the angle on the white paper and the color change depending on the angle on the black paper, and in Example 8, the handwriting was
Both the color change depending on the angle on the white paper and the color change depending on the angle on the black paper were the color changes from orange to green. On the other hand, in Comparative Example 5, which is an ink composition containing the viewing angle-dependent polychromatic particles A and the green pigment without containing the pearl pigment A, the handwriting has a color change from green to pink on the white paper depending on the angle. However, the color change depending on the angle on the black paper was from red to yellow, and as compared with Comparative Example 1, the original color change on the viewing angle-dependent polychromatic particles A and the color change on the black paper were the same. Further, in Comparative Example 6 containing the viewing angle-dependent polychromatic particles A and the green dye without containing the pearl pigment A, the color change depending on the angle on the white paper is pink to orange, but the color depending on the angle on the black paper is changed. The change was from red to yellow, and as compared with Comparative Example 1, the original color change of the viewing angle-dependent polychromatic particles A and the color change on black paper were the same. That is,
A viewing angle-dependent multicolored ink composition containing viewing angle-dependent multicolored particles, a pearl pigment and a dark colorant is a viewing angle-dependent multicolored particle containing no pearl pigment and containing a dark colorant. Compared with a color ink composition, it is possible to obtain a view angle-dependent polychromatic handwriting with different color changes on white paper and black paper.

Example 4 is a viewing angle dependent pleochroic ink composition containing viewing angle dependent pleochroic particles A, pearl pigment B and a black dye. In Example 4, the handwriting is a color change from purple to silver in both the color change depending on the angle on the white paper and the color change depending on the angle on the black paper, which is different from that in Example 2 because the pearl pigment is different. You can get handwriting of color change.

Example 5 is a viewing angle dependent polychromatic ink composition containing viewing angle dependent polychromatic particles B, pearl pigment A and a black dye. In Example 5, in the handwriting, the color change with angle on white paper is from brown to green, and the color change with angle on black paper is from orange to green. The angle-dependent color change of the viewing angle-dependent pleochroic ink composition of Example 5 on black paper shows that the viewing angle-dependent pleochroism of Comparative Example 7 contains the viewing angle-dependent pleochroic particles B and the black dye. Compared with the color change of the ink composition on black paper depending on the angle, it shows a color change from yellow green to brown, unlike the color change from red to orange, which is the original color change of the viewing angle-dependent polychromatic particles B. It was In addition, the viewing angle-dependent polychromatic ink composition of Example 5
Even on a white paper, the color change depending on the angle showed a color change different from the original color change of the viewing angle-dependent polychromatic particles B.

Example 6 is a viewing angle dependent polychromatic ink composition containing viewing angle dependent polychromatic particles C, pearl pigment C and a black dye. In Example 6, in the handwriting, the color change depending on the angle on the white paper is the color change from brown to green, the color change depending on the angle on the black paper is the color change from orange to green, and the visual angle-dependent multicolor Even if the luminescent particles and the pearl pigment are different, it is possible to obtain a handwriting with a color change different from the original color change of the viewing angle-dependent polychromatic particles. In addition, the change in color depending on the angle on the black paper of the viewing angle-dependent polychromatic ink composition of Example 6 included the viewing angle-dependent polychromatic particles C and the black dye, and the viewing angle-dependent polychromatic ink of Comparative Example 8 containing no pearl pigment. Compared with the color change of the color ink composition depending on the angle on the black paper, the color change from red to green is different from the color change from yellow to green which is the original color change of the viewing angle dependent polychromatic particles C. Indicated. In addition, the viewing angle-dependent polychromatic ink composition of Example 6 showed a color change on white paper which was different from the original color change of the viewing angle-dependent polychromatic particles C.

Regarding the uniformity of handwriting, the first embodiment
6 to 6 were all good, while the writing uniformity was non-uniform in Examples 7 and 8, and the writing uniformity was non-uniform in Comparative Examples 5 and 6. In Examples 7 and 8, although the writing uniformity was non-uniform, it was possible to observe a color change different from the original color change of the viewing angle dependent polychromatic particles not only on the white paper but also on the black paper.

Furthermore, since the viewing angle-dependent multicolor ink compositions of Examples 2 to 8 contain a dark colorant, the viewing angle-dependent multicolor ink of Example 1 does not contain a dark colorant. The handwriting was easier to see and the change in color was easier to confirm than the functional ink composition. In particular, with respect to the viewing angle dependent polychromatic ink compositions of Examples 2 to 6 in which the black colorant was used as the dark colorant, more uniform handwriting was obtained.

[0064]

EFFECTS OF THE INVENTION The viewing angle-dependent polychromatic composition of the present invention contains the viewing angle-dependent polychromatic particles and the pearl pigment, so that a color change different from the original color change possessed by the viewing angle-dependent polychromatic particles. By using the viewing-angle-dependent polychromatic composition in inks, resin-forming products, paints, paints, cosmetics, stamp inks, handwriting, coating film, formation having a desired color change depending on the viewing angle can be obtained. Things can be obtained. In particular, it can be suitably used for writing implements such as ballpoint pens, stamps and paints, and facial cosmetics,
It can be used for cosmetics such as make-up cosmetics and hair cosmetics, and particularly preferably for nail polish, pedicure, nail polish, mascara, eyeliner, eye shadow, lipstick, blusher, foundation and the like.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) A61K 7/032 A61K 7/032 7/04 7/04 7/06 7/06 B43K 7/00 B43K 7 / 00 8/02 C09D 11/16 C09D 11/16 B43K 8/02 AF (72) Inventor Kyoko Sano 1-6-20 Morinomiyachuo, Chuo-ku, Osaka City, Osaka Prefecture F-term in Sakura Crepas Co., Ltd. (reference) 2C350 GA03 GA04 HA08 HA15 NA19 4C083 AB171 AB221 AB231 AB241 AD211 AD491 BB21 CC03 CC11 CC12 CC13 CC14 CC28 CC31 4J037 AA15 AA22 AA24 CA09 CA24 EE03 FF03 FF09 4J039 AB01 BE01 BE02 BE12 BE22 CA03 EA14 GA26 GA27

Claims (8)

[Claims] 1. A viewing angle dependent pleochroic composition comprising at least viewing angle dependent pleochroic particles and a pearl pigment. 2. The viewing angle-dependent polychromatic particles (a) include a substrate layer and a coating layer in the particles, wherein the substrate layer or the coating layer is at least a silicon compound, an iron compound, an aluminum compound, and a titanium oxide. The viewing angle dependent pleochroic composition according to claim 1, which is a viewing angle dependent pleochroic particle containing any one of the compounds, or (b) a viewing angle dependent pleochroic particle containing a cholesteric liquid crystal polymer. 3. The view-angle-dependent pleochroic composition according to claim 1, which contains a dark colorant. 4. The viewing angle-dependent pleochroic composition according to claim 1, which contains a polysaccharide. 5. The viscosity range is 500 to 15000 mPa · s as measured by an E-type viscometer (3 ° R14 cone, rotation speed: 0.5 rpm, 20 ° C.). The viewing angle dependent pleochroic composition of. 6. An ink composition for a writing instrument, which uses the view-angle-dependent pleochroic composition according to any one of claims 1 to 5. 7. Visual-angle-dependent polychromatic particles 0.5 to 40% by weight, pearl pigments 0.5 to 40% by weight, and polysaccharides 0.0.
An ink composition for a writing instrument containing 1 to 20% by weight. 8. A writing instrument containing the ink composition for a writing instrument according to claim 6 or 7 in an ink containing portion.