JP2002097402A - Glittering aqueous ink composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a glittering aqueous ink composition used for a ball-point pen, or the like, which can obtain handwriting having strong glittering feeling compared with aqueous ink compositions using a conventional aluminum powder pigment or a pearl pigment. SOLUTION: This glittering aqueous ink composition comprises the following components (a) to (e) and whose viscosity is 1,000 to 10,000 mPa.s (by using an ELD type viscometer: at 3 deg. R14 cone, 0.5 rpm, and at 20 deg.C): (a). 0.01-20 wt.% of an aluminum powder pigment having not less than 15 μm of a median size when ground and treated by using oleic acid or stearic acid as a grinding auxiliary agent; (b). 0.1-40 wt.% of a synthetic resin emulsion selected from an acrylic resin emulsion, a styrene-acrylic resin emulsion and a vinyl acetate resin emulsion; (c). 0.01-40 wt.% of a polysaccharide selected from Wellan gum, succinoglucan and Ramsan gum; (d). 1-40 wt.% of an aqueous organic solvent; and (e). 0.05-15 wt.% of a coloring pigment.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a brilliant aqueous ink composition which can be suitably used for a ballpoint pen.

[0002]

2. Description of the Related Art Conventionally, there has been provided an aqueous ink composition using a brilliant pigment in order to obtain a handwriting of a metallic gloss color such as gold or silver. For example, Japanese Patent Application Laid-Open No. 8-15147
An aqueous ink composition using an aluminum powder pigment surface-treated with stearic acid. JP-A-7-118592
No. is an aqueous ink composition using a pearl pigment.

[0003]

However, in the case of such an aqueous ink composition using the conventional aluminum powder pigment or pearl pigment, it has been difficult to obtain a handwriting having a strong glitter. An object of the present invention is to provide a glittering aqueous ink composition used for a ballpoint pen or the like which can obtain a handwriting having a strong glittering feeling as compared with a conventional aqueous ink composition using an aluminum powder pigment or a pearl pigment. There.

[0004]

Means for Solving the Problems As a result of intensive studies to achieve the above object, an aluminum powder pigment pulverized by using oleic acid as a pulverization aid and having a median diameter of 15 μm or more, preferably 30-60μ
In the case of an aluminum powder pigment of m, a water-soluble resin, a water-soluble organic solvent and water-based ink composition containing the same together with water as a water-based ink composition for writing instruments such as ball-point pens, the handwriting of the ink exhibits a strong glitter. I found it.

[0005] Further, even in the case of an aluminum powder pigment which has been pulverized using stearic acid as a pulverization aid and has a median diameter of 15 µm or more, preferably 30 to 60 µm, it can be treated with a water-soluble resin. It has been found that a water-based ink composition containing a water-soluble organic solvent and water, when used in a writing instrument such as a ball-point pen, exhibits a strong glitter in the handwriting of the ink.

[0006] Since the aqueous ink composition of the present invention is as described above, when written using a writing instrument such as a ball-point pen, the handwriting exhibits a strong glittering feeling.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION (Aluminum powder pigment) The aluminum powder pigment used in the present invention is obtained by mixing oleic acid or stearic acid as a grinding aid together with mineral spirit, dispersing the mixture, and then pulverizing with a ball mill. As an aluminum paste. For example, preferably, the aluminum paste (cake) is further added to a mixer together with an inorganic phosphoric acid, an aliphatic compound, a surfactant, water, a hydratable alcohol, and a hydrocarbon oil, and then kneaded. Type aluminum flake paste (water-resistant aluminum powder pigment or water-resistant aluminum flake pigment composition) can also be used. In short, any aluminum powder pigment that has been pulverized using oleic acid or stearic acid as a pulverization aid can be used.

In the case of an aluminum powder pigment pulverized by using this oleic acid as a pulverizing aid, non-leafing is performed because the adsorption of oleic acid to the particle surface of the aluminum powder pigment is coarse and the polarity is large. As a type of handwriting or coating, the aluminum powder pigment is present in the handwriting or coating so that each aluminum powder pigment is oriented at various angles. On the other hand, instead of the oleic acid, if the aluminum powder pigment is pulverized using stearic acid as a grinding aid in the same manner as oleic acid, the adsorption of stearic acid on the particle surface of the aluminum powder pigment becomes dense. And the polarity is low, so that it is a leafing type handwriting or coating. In such a case, since the aluminum powder pigment is gathered on the handwriting or the surface of the coating film, the pigment particles of each aluminum powder are oriented substantially parallel to the handwriting or the coating film surface. However, by containing a polar resin (varnish), as in the case of the above-mentioned aluminum powder pigment pulverized using oleic acid as a pulverization aid, the aluminum powder pigment becomes a non-leafing type handwriting or coating film. Is present in the handwriting or coating film, so that each aluminum powder pigment is oriented at various angles. That is, in the case of an aluminum powder pigment pulverized using stearic acid as a pulverization aid, it is important to contain a resin having a high polarity or oxidation that makes the aluminum powder pigment non-leafing. As these resins,
A water-soluble resin such as an alkyd resin or a melamine resin which has been subjected to electrolysis with a basic neutralizing agent, introduction of a hydroxyl group or an ether group and the like, and hydroxylation can be exemplified.

Further, in the present invention, in order to express a strong glitter to handwriting of a ball-point pen or the like, the pigment particles are preferably made of aluminum powder pigment having a large median diameter of 15 μm or more, preferably 30 to 60 μm. is important.
When the median diameter of the aluminum powder pigment is less than 15 μm, even if the aluminum powder pigment is oriented in non-leafing in the handwriting or the coating film, the flake particles are too small as the handwriting of the ballpoint pen ink, resulting in poor brightness. . On the other hand, if the median diameter of the aluminum powder pigment is more than 60 μm, it is not preferable even if the content of the aluminum powder pigment or the ball diameter is adjusted, because it hardly comes out of the pen tip when used as a ballpoint pen ink. In addition, if the particle diameter of the large-diameter aluminum powder pigment is 30 μm or more than 30 μm, the handwriting will exhibit even stronger glitter.

As such aluminum powder pigments,
For example, Asahi Kasei's product name “AW7000R” (median diameter: 15 μm), Toyo Aluminum's product name “WXM7640” (median diameter: 17 μm), and product name “WXM5422” (median diameter: 19 μm)
m), product name “WXM1440” (median diameter: 30 μm) manufactured by the company, product name “WXM1415” manufactured by the company
(Median diameter: 51 μm), brand name “WXM7”
493 "(median diameter: 60 μm). These aluminum powder pigments having different median diameters can be used alone or in combination of two or more.

In the present invention, the “median diameter” is defined as
It shows the diameter specified by the D50 value by a laser diffraction type particle size distribution meter.

It is preferable that such a large-diameter aluminum powder pigment is contained in the ink composition in an amount of 0.01 to 20% by weight based on the total amount of the ink composition. When the amount of the aluminum powder pigment is less than 0.01% by weight based on the total amount of the ink composition, the glitter is insufficient. If the amount of the aluminum powder pigment exceeds 20% by weight in the total amount of the ink composition, the viscosity of the ink becomes too high, the fluidity is reduced, and the writing property is reduced. When applied as an ink for a ballpoint pen, the optimum amount of such a large particle size aluminum powder pigment is determined in consideration of both glitter and ink outflow (ink outflow between a ball and a socket holding the ink). Then, it is 0.05 to 10% by weight.

(Water-soluble resin) As the water-soluble resin, a water-soluble thickening resin capable of adjusting the viscosity of the ink and preventing the dispersion and sedimentation of the aluminum powder pigment and the colorant having a large particle diameter can be achieved. It is important to use a water-soluble resin that imparts pseudoplastic flow characteristics (thixotropic properties) to the ink. For example, microbial polysaccharides and derivatives thereof are used. For example, pullulan, xanthan gum, welan gum, ramzan gum, succinoglucan, dextran and the like can be exemplified. In addition, water-soluble plant polysaccharides and derivatives thereof are used. For example, tragansi gum, guar gum, tara gum, locust bean gum, gati gum, arabinogalactan gum, gum arabic, quisse gum, pectin, starch, syrup bee gum, carrageenan, alginic acid, agar, etc. are exemplified. can do. In addition, water-soluble animal polysaccharides and derivatives thereof are used. For example, gelatin, casein, and albumin can be exemplified. Further, N-vinylacetamide resin, cross-linked N
-N-vinylacetamide resins such as vinylacetamide resins can be used.

In the present invention, among the above-mentioned water-soluble resins, microbial polysaccharides and derivatives thereof are preferably used. The above-mentioned water-soluble resins can be used alone or in combination of two or more.

These water-soluble resins are preferably contained at 0.01 to 40% by weight in the total amount of the ink composition.
When the amount of the water-soluble resin is less than 0.01% by weight based on the total amount of the ink composition, the effect of preventing the aluminum powder pigment having a large particle size from settling is insufficient. If the amount of the water-soluble resin exceeds 40% by weight in the total amount of the ink composition, the viscosity of the ink becomes too high, and the fluidity decreases. The optimum amount of the water-soluble resin varies slightly depending on the type of the water-soluble resin, but is 0.05 to 20% by weight.
It is.

Among the above water-soluble resins, in particular,
Welan gum, ramzan gum, and succinoglucan have good dispersion stability in ink with respect to aluminum powder pigments having a median diameter of 15 μm or more, preferably 30 to 60 μm, and have a large particle diameter. Good pseudoplastic flow characteristics (thixotropic properties) can be imparted to inks containing.

(Water-soluble organic solvent) It is preferable to use a water-soluble organic solvent which can prevent drying at the pen tip and freezing of the ink. For example, ethylene glycol, diethylene glycol, triethylene glycol
Glycols such as propylene glycol and polyethylene glycol, polyhydric alcohols such as glycerin, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, and dipropylene glycol monopropyl. Glycol ethers such as ethers can be exemplified. These organic solvents can be used alone or in combination of two or more.

The water-soluble organic solvent is used in the total amount of the ink composition.
Preferably, it is contained in an amount of up to 40% by weight. When the amount of the water-soluble organic solvent is less than 1% by weight based on the total amount of the ink composition, the pen tip is easily dried and the ink is easily frozen.
When the amount of the water-soluble organic solvent exceeds 40% by weight in the total amount of the ink composition, it affects the solubility of the water-soluble resin,
Handwriting is difficult to dry. The optimal blending amount of the water-soluble organic solvent slightly varies depending on the type of the water-soluble organic solvent, but is 5 to 20% by weight.

(Colorant) As the colorant, those which do not react with the above-mentioned aluminum powder pigment having a large particle size and do not affect the glitter of the aluminum powder pigment are preferred.
Specifically, in addition to water-soluble dyes such as acid dyes, direct dyes, and basic dyes, inorganic pigments such as carbon black, copper phthalocyanine-based pigments, selen-based pigments, azo-based pigments, quinacridone-based pigments, and anthraquinone-based pigments And organic pigments such as dioxane pigments, indigo pigments, thioindigo pigments, perinone pigments, perylene pigments, indolenone pigments, and azomethine pigments, as well as fluorescent pigments and colored resin emulsions. These can also be used as a pigment dispersion. In the present invention, the pigments can be used alone or in combination of two or more.
In addition, the large-diameter aluminum powder pigment of the present invention can be used in combination with a glitter pigment such as a pearl pigment. Further, it is used by being mixed with a concealing pigment such as various inorganic or organic white pigments such as opaque titanium oxide, alkylenebismelamine derivatives, plastic pigments (synthetic resin particle pigments) of various shapes such as spherical and flat shapes. You can also. Further, an aluminum powder pigment can be used together with a metal-coated inorganic pigment.

In the aqueous ink composition of the present invention, a coloring agent may not necessarily be contained. Even an aqueous ink composition that does not contain a colorant but contains an aluminum powder pigment can give a strong glitter to handwriting. However, the water-based ink composition containing a colorant is extremely preferable because it can give a strong shine according to the hue or the like to the handwriting depending on the hue or the like of the colorant.

The colorant is used in an amount of 0.1% in the total amount of the ink composition.
It is preferable that the content is from 0.5 to 15% by weight. When the amount of the coloring agent is less than 0.05% by weight in the total amount of the ink composition, it is difficult to visually recognize the coloring of the coloring agent. If the amount of the coloring agent exceeds 15% by weight based on the total amount of the ink composition, the viscosity of the ink becomes too high, and the fluidity decreases. The optimal amount of the coloring agent is
Although slightly different depending on the type of the coloring agent, it is 1 to 10% by weight.

(Synthetic Resin Emulsion) As described above, in order to obtain a handwriting having a strong glitter, the present inventor added oleic acid and oleic acid to an ink composition containing a water-soluble thickening resin, a water-soluble organic solvent and water. Alternatively, it has been found that it is preferable to use a large-diameter aluminum powder pigment pulverized using stearic acid as a pulverization aid. The use of this large-diameter aluminum powder pigment imparts a stronger shine to handwriting compared to a small-particle-size aluminum powder pigment or pearl pigment that has been pulverized using another fatty acid or inorganic acid as a grinding aid. Can be.

However, in a glitter aqueous ink composition containing a water-soluble resin, particularly a water-soluble thickening resin, it is possible to enhance the fixability of the aluminum powder pigment having a large particle diameter to some extent by the water-soluble thickening resin. However, it has been found that it is difficult for the water-soluble thickening resin to strongly fix the large-diameter aluminum powder pigment to the substrate because the large-diameter aluminum powder pigment has a large shape. Therefore, in the aqueous ink composition containing the above-described large-particle-size aluminum powder pigment, after writing, the large-particle-size aluminum powder pigment is easily peeled off due to friction or the like, and it is difficult to continuously give a strong glitter to handwriting, The durability of handwriting having a brilliant feeling is low.

From the above, without deteriorating the ink properties and writing suitability, and without impairing the effect of the strong glittering effect by the above-mentioned large particle size aluminum powder pigment,
An aqueous ink composition that can improve the fixability of the above-mentioned large-diameter aluminum powder pigment to a base material and can continue to give a stronger shine to handwriting, particularly a brilliant aqueous ink composition for writing implements, especially for ballpoint pens Providing things is an important issue.

As a result of intensive studies to achieve the above object, the above-mentioned aluminum powder pigment having a large particle diameter, a water-soluble resin, a water-soluble organic solvent and water as essential components, and the above-mentioned aluminum powder pigment having a large particle diameter, The inventors have found that a glittering aqueous ink composition containing a binder component (fixing resin component) for fixing to a substrate such as an object to be coated such as paper or an object to be transferred or the like can solve the above problems. Was.

On the other hand, in order to strongly fix such a large-diameter aluminum powder pigment to a substrate such as an object to be coated or an object to be transferred, it is conceivable to use a water-soluble synthetic resin as a binder component. However, if the content of the water-soluble synthetic resin is increased depending on the type of the water-soluble synthetic resin in order to strongly fix the large-diameter aluminum powder pigment, the solubility of the thickening resin and the dispersibility of the colorant may be adversely affected. In addition, the viscoelasticity of the ink may be significantly reduced, and writing suitability may be reduced. Further, even if the fixing property to a substrate such as an object to be coated and an object to be transferred is exhibited, the water-based ink composition should not be such that the strong glitter of the large-diameter aluminum powder pigment is reduced in the handwriting.

The present inventors have conducted further intensive studies, and as a result,
When a synthetic resin emulsion is used as a binder component for fixing the large-diameter aluminum powder pigment to a substrate such as an object to be coated and an object to be transferred, without losing glitter,
For example, the inventors have found that the fixability of the large-diameter aluminum powder pigment to a base material such as paper such as writing paper can be improved, and completed the present invention.

Therefore, the aqueous ink composition of the present invention containing the above-mentioned aluminum powder pigment having a large particle diameter can be used on a substrate such as paper, metal, plastics, textiles, etc. to be coated or transferred by using the aqueous ink composition. When writing, coating, or transferring to a substrate, the fixability of the large-diameter aluminum powder pigment to a substrate such as an object to be applied or an object to be transferred can be enhanced, and a durable handwriting can be obtained. That is, the handwriting can continue to be given a strong glittering feeling. This is because the film forming property of the synthetic resin emulsion is suitable for the large-grain aluminum powder pigment having a large flake shape, without impairing the effect of strong glitter by the large-grain aluminum powder pigment. This is because the toner can be strongly fixed to a substrate such as an object to be coated and an object to be transferred.

Further, since the binder component (fixing resin component) of the present invention is not a water-soluble synthetic resin but a synthetic resin emulsion, the solubility of the water-soluble thickening resin and the dispersibility of the colorant are simultaneously added. And adversely affect properties such as viscoelasticity of the ink. Therefore, the ink composition of the present invention can improve the fixability of the aluminum powder pigment having a large particle diameter without affecting the viscosity, writing suitability, and handwriting color of the ink.

From the above, the glitter aqueous ink composition containing the above-mentioned aluminum powder pigment having a large particle diameter according to the present invention provides a high surface smoothness of glass without deteriorating the ink properties and writing suitability. Without affecting the ink composition, it is possible to continue to give the handwriting a stronger brilliant feeling as compared with the aqueous ink composition using a brilliant pigment such as a conventional aluminum powder pigment or a pearl pigment.

The synthetic resin emulsion of the present invention includes:
There is no particular limitation, and any water-dispersible synthetic resin emulsion can be used. However, in consideration of ink properties and writing suitability, it is important to use one that does not affect the solubility of the water-soluble thickening resin, the viscosity of the ink, the dispersibility of the colorant, and the coloring of the ink. In addition, it is important that the effect of the strong glittering effect by the above-mentioned large particle size aluminum powder pigment is not impaired.

The minimum film forming temperature of the synthetic resin emulsion is preferably 20 ° C. or lower. When the minimum film-forming temperature of the synthetic resin emulsion is 20 ° C. or lower, particularly 0 ° C. or lower, the film can be formed not only at room temperature (about 25 ° C.) but also in a cold region, and the fixability of handwriting to the base material can be enhanced.

As the synthetic resin emulsion, those having anionic or nonionic properties can be suitably used. An anionic or nonionic synthetic resin emulsion can be obtained, for example, by preparing a synthetic resin from an anionic or nonionic monomer, or by using an anionic or nonionic emulsifier. When the synthetic resin emulsion has anionic or nonionic properties, the stability of the ink composition can be enhanced.

Further, the synthetic resin emulsion has a
When H is 6 or more, those which do not affect the dispersibility of the colorant and the solubility of the water-soluble thickening resin are preferable.

From such a viewpoint, as the synthetic resin emulsion, for example, an acrylic synthetic resin emulsion, a styrene-acrylic synthetic resin emulsion, and a vinyl acetate synthetic resin emulsion can be used.
Further, as the acrylic synthetic resin emulsion, for example, an acrylic ester copolymer synthetic resin emulsion is suitable. As the styrene-acrylic synthetic resin emulsion, for example, a styrene-acrylate copolymer synthetic resin emulsion is preferable. Further, as the vinyl acetate-based synthetic resin emulsion, for example, a vinyl acetate synthetic resin emulsion or a vinyl acetate-acrylate copolymer synthetic resin emulsion is preferably used. The synthetic resin emulsion can be used alone or as a mixture of two or more of these synthetic resins.

Specifically, as an acrylic synthetic resin emulsion, for example, the trade name “Nicazole FX33”
6 "(manufactured by Nippon Carbide Industry Co., Ltd., minimum film forming temperature <
0 ° C, pH 7.5, 200 mPa · s), trade name “Nicazole A-02” (manufactured by Nippon Carbide Industry Co., Ltd., minimum film formation temperature <0 ° C, pH 7.0, 500 mPa · s),
Trade name “Nicazole FH-011A” (manufactured by Nippon Carbide Industry Co., Ltd., minimum film formation temperature <0 ° C., pH 7.0, 1
50 mPa · s), and as a vinyl acetate-based synthetic resin emulsion, for example, trade name “Movinyl 231”
(Made by Clariant Polymer Co., Ltd., minimum film formation temperature <0
° C, pH 4.0, and viscosity of 500 to 1500 mPa · s). This viscosity measurement is a numerical value measured by a B-type viscometer at 25 ° C.

Although the content of the synthetic resin emulsion is not particularly limited, for example, the preferred range is 0.1 to 40% by weight in terms of solid content based on the total amount of the ink composition. When the content of the synthetic resin emulsion is less than 0.1% by weight in terms of solid content with respect to the total amount of the ink composition, the fixability of the large-particle-size aluminum powder pigment to a substrate is reduced. On the other hand, when the content of the synthetic resin emulsion exceeds 40% by weight in terms of solids with respect to the total amount of the ink composition, the solids content increases and the writing aptitude decreases due to coating with a pen tip. In addition, handwriting becomes easy to whiten. In order to further improve the fixability of the large-diameter aluminum powder pigment to the substrate, the content of the synthetic resin emulsion should be at least 0.3% by weight in solid content with respect to the total amount of the ink composition. It is the best. In order to further improve the writeability, the content of the synthetic resin emulsion is optimally set to 20% by weight in solid content based on the total amount of the ink composition. That is, the optimal content of the synthetic resin emulsion,
0.3 to 20% by weight.

As described above, the glitter aqueous ink composition according to the embodiment of the present invention contains the following components a to e with respect to the total amount of the ink and has a viscosity of 1,000 to 1
The brilliant aqueous ink composition according to claim 1, which has a viscosity of 000 mPa · s (ELD viscometer: 3 ° R14 cone, 0.5 rpm, 20 ° C.). a. 0.01 to 20% by weight of an aluminum powder pigment having a median diameter of 15 μm or more pulverized by using oleic acid and / or stearic acid as a pulverization aid; b. 0.1 to 40% by weight of a synthetic resin emulsion selected from an acrylic resin emulsion, a styrene-acrylic resin emulsion and a vinyl acetate resin emulsion
(Solid content), c. 0.01 to 40% by weight of a polysaccharide selected from welan gum, succinoglucan and ramzan gum; d. 1 to 40% by weight of a water-soluble organic solvent, e. Coloring pigment 0.05 to 15% by weight

(Other Additives) In the present invention, if necessary, lubricants such as polyoxyethylene alkali metal salts, dicarboxylic acid amides, phosphate esters, N-oleyl sarcosine salts, benzotriazole, tolyl Rust inhibitors such as triazole dicyclohexylammonium nitrate, antiseptic and fungicides such as benzoisothiazoline, pentachlorophenol and cresol, and various surfactants for the aluminum powder pigment having the above-mentioned large particle size can be added.

The preferred viscosity range of the ink composition of the present invention is 1,000 to 10,000 mPa · s. The ink composition of the present invention is adjusted to such a viscosity range. The viscosity is a value measured by an ELD viscometer (3 ° R14 cone, rotation speed: 0.5 rpm, 20 ° C.).

(Method for preparing ink) Ink can be prepared by a conventionally known dispersing method, defoaming method, filtration, etc., but the following method is preferred as a charging method. That is, after dispersing water, a water-soluble organic solvent, a glittering aluminum powder pigment and a colorant with a dissolver or the like at room temperature, adding a water-soluble resin and a fixing resin, and adding various additives as necessary, The pH is adjusted if necessary, and the resulting solution is filtered by pressure filtration or the like, and then defoamed to obtain a glitter ink composition.

[0042]

EXAMPLE With the composition and blending amount (% by weight) shown in Table 1, each component such as water, a water-soluble organic solvent, a predetermined large-diameter aluminum powder pigment, and a colorant or pigment base was prepared according to the above-mentioned production method. After mixing and stirring and dispersing, throw in the water-soluble resin,
This was filtered and then defoamed to obtain a brilliant aqueous ink composition of Example. Further, as shown in Table 2, for comparison, components such as water, a water-soluble organic solvent, an aluminum powder pigment having a small particle diameter and a pearl pigment were mixed, stirred and dispersed, and then a water-soluble resin was added. Was filtered and then defoamed to obtain a water-based ink composition of Comparative Example. In each case, a conventionally known method was used for the dispersion method, the defoaming method, the filtration and the like.

[0043]

[Table 1]

[0044]

[Table 2]

In the table, the composition of each raw material is as follows. (Aluminum powder pigment) I: Oleic acid-treated aluminum powder pigment, trade name "WX
M5422, manufactured by Toyo Aluminum Co., Ltd., median diameter 19 μm II: oleic acid-treated aluminum powder pigment, trade name “WX
M1440, manufactured by Toyo Aluminum Co., Ltd., median diameter 30 μm III: oleic acid-treated aluminum powder pigment, trade name “W
XM1415 ", manufactured by Toyo Aluminum Co., Ltd., median diameter 51 μm IV: Stearic acid-treated aluminum powder pigment, trade name" W
XM0630 ", manufactured by Toyo Aluminum Co., Ltd., median diameter 7 μm V: Stearic acid-treated aluminum powder pigment, trade name" 1
110W ", manufactured by Showa Aluminum Co., Ltd., median diameter 15μm

(Pearl pigment) trade name "Iriodin 302",
Merck Japan Co., Ltd., median diameter about 5-20 μm

(Water-soluble resin) I: welan gum, trade name "K1C376", manufactured by Sansei Co., Ltd. II: succinoglucan, trade name "Reozan", Sansei Co., Ltd. III: ramzan gum, trade name "K7C233", IV: Amine neutralized alkyd resin, trade name "Watersol S-311", manufactured by Dainippon Ink and Chemicals, Inc.

(Water-soluble organic solvent) I: glycerin II: propylene glycol

(Fixing Resin) I: Acrylic synthetic resin emulsion (trade name “Nicazole FH-011A” (manufactured by Nippon Carbide Industrial Co., Ltd., minimum film forming temperature <0 ° C., pH 7.0, 150 mPa · s)
s (Measurement value of B-type viscometer at 25 ° C.)) II: Acrylic synthetic resin emulsion (trade name “Nicazole FX-336”, manufactured by Nippon Carbide Industrial Co., Ltd., pH
7.5, minimum film formation temperature <0 ° C, viscosity 200 mPa · s
(Measured value of B-type viscometer at 25 ° C.)

(Coloring agent) I: Blue pigment base A blue pigment-based pigment dispersion is prepared by dissolving a mixture of the following blue pigment and the following pigment dispersing resin in the following ratio by adding triethylamine. Dispersed by ball mill, average particle size 0.08 μm, solid content concentration 10% by weight
As an aqueous pigment dispersion. As a blue pigment, phthalocyanine blue (trade name “Fast Gen Blue TG”
R "(manufactured by Dainippon Ink and Chemicals, Inc.), and a styrene-acrylic copolymer (trade name" John Krill ") as a pigment dispersing resin
J683 ", manufactured by Johnson Polymer, weight average molecular weight: 8000). Phthalocyanine blue 5 parts by weight Pigment dispersing resin 1 part by weight II: Red dye (Acid Red 289, trade name "Chugai Am
inol Pink R ", manufactured by Chugai Chemicals)

(Antiseptic / antifungal agent) 1,2-benzisothiazolin-3-one (trade name: "Proxel GXL", manufactured by Hoechst Gosei Co., Ltd.)

(Rust inhibitor) Benzotriazole

(Lubricant) POE alkyl ether phosphate (phosphate ester activator, trade name "Phosphanol PE-510", manufactured by Toho Chemical Industry Co., Ltd.)

(Glitter pigment dispersant such as aluminum powder pigment) POE nonylphenyl ether (nonionic surfactant, HLB: 13.2, trade name "Emulgen PI-2")
0T ", manufactured by Kao Corporation)

(Preparation of Test Sample) Next, each of the ink compositions of the examples and comparative examples shown in the table was applied to polypropylene having a stainless steel ball pen tip (ball material: silicon carbide) connected at one end. Was filled in an ink storage section composed of a hollow shaft cylinder made of the same, and a ball-point pen of each test sample loaded with the ink storage section was prepared.

(Evaluation Test) The ballpoint pens were used to write on commercially available loose-leaf paper, and the glitter of each ink composition was evaluated for the examples and comparative examples shown in Table 1. The glitter was evaluated by visually observing the written state, and evaluated as ○ when the glitter was strong, and as X when the glitter was small or no glitter. From the table, in all of Examples 1, 6, 8, 10 and 13, handwritings exhibiting glittering images of jewel diamonds were obtained. Examples 2, 4, 9, 1
In each of Nos. 1 and 14, handwritings exhibiting glittering images of the aquamarine gem were obtained. Examples 3, 5,
In all of 7, 12, and 15, handwritings exhibiting glittering images of pearl pink of jewels were obtained. On the other hand, in each of the comparative examples, handwriting having a strong whiteness was obtained, and no glitter was exhibited. In particular, the ink compositions of the examples were scattered with brilliantly bright spots as compared with Comparative Examples 7, 10, 11 and 12 containing pearl pigments, irrespective of the presence or absence of the fixing resin. Handwriting was obtained.

The above example was applied as an ink composition for a ballpoint pen, but contained an aluminum powder pigment having a median diameter of 15 μm or more, which was pulverized using oleic acid and / or stearic acid as a pulverization aid. The glitter ink composition of the present invention can be used for other writing instruments. Further, as long as the glittering ink composition of the present invention contains an aluminum powder pigment having a median diameter of 15 μm or more pulverized using oleic acid and / or stearic acid as a pulverization aid, facial cosmetics, nail polish, pedicure, Nail polish,
It can also be used in cosmetics-related fields for various uses such as makeup cosmetics such as mascara, eyeliner, eye shadow, lipstick, foundation, and hair cosmetics.

[0058]

According to the present invention, an aluminum powder pigment having a median diameter of 15 μm or more, preferably 30 to 60 μm, which has been pulverized by using oleic acid and / or stearic acid as a pulverization aid, a water-soluble resin, a water-soluble organic solvent And because it is a glittering aqueous ink composition containing at least water, compared to the aqueous ink composition using a conventional glittering pigment,
Unprecedented unique handwriting with stronger glitter can be obtained. In particular, in the case of the above glittering aqueous ink composition containing a coloring agent together with the aluminum powder pigment, it is possible to give a strong handwriting to the handwriting according to the hue of the coloring agent.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Yuki Yamamoto 1-6-20 Morinomiya Chuo, Chuo-ku, Osaka-shi, Osaka Inside Sakura Crepas Co., Ltd. (72) Inventor Tomohiro Sawa 1-6-6 Morinomiya Chuo, Chuo-ku, Osaka-shi, Osaka No. 20 F-term in Sakura Crepas Corporation (reference) 4J039 AB01 AD03 AD08 AD09 BA06 BC19 BE01 BE12 CA06 EA21 FA01 FA02 FA03 GA27

Claims (7)

[Claims] 1. A brilliant aqueous ink containing at least an aluminum powder pigment having a median diameter of 15 μm or more, which has been pulverized using oleic acid and / or stearic acid as a pulverization aid, a water-soluble resin, a water-soluble organic solvent, and water. Composition. 2. The glitter aqueous ink composition according to claim 1, wherein the aluminum powder pigment is an aluminum powder pigment having a median diameter of 30 to 60 μm. 3. The method according to claim 1, wherein the aluminum powder pigment is contained in an amount of 0.01 to 20% by weight based on the total amount of the ink.
The brilliant aqueous ink composition as described in the above. 4. The brilliant aqueous ink composition according to claim 1, which comprises a synthetic resin emulsion as a binder component for fixing the aluminum powder pigment to a substrate. 5. A synthetic resin emulsion having a solid content of 0.1%.
The brilliant aqueous ink composition according to claim 4, which is contained in an amount of from 40 to 40% by weight. 6. The ink contains the following components a to e with respect to the total amount of the ink, and has a viscosity of 1,000 to 10,000 mPa · s.
(ELD viscometer: 3 @ R14 cone, 0.5 rpm,
(20 ° C.). a. 0.01 to 20% by weight of aluminum powder pigment having a median diameter of 15 μm or more ground using oleic acid and / or stearic acid as a grinding aid, b. 0.1 to 40% by weight of a synthetic resin emulsion selected from an acrylic resin emulsion, a styrene-acrylic resin emulsion and a vinyl acetate resin emulsion
(Solid content), c. 0.01 to 40% by weight of a polysaccharide selected from welan gum, succinoglucan and ramzan gum; d. 1 to 40% by weight of a water-soluble organic solvent, e. Coloring pigment 0.05 to 15% by weight 7. A ball-point pen filled with the aqueous ink having pseudoplastic fluidity according to claim 6.