JP2003026985A - Brilliant ink composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a brilliant ink composition having an excellent storage stability and capable of obtaining a hand or a coating film with a brilliant sense and a stereoscopic effect in which reflection points having various colors and luminance are inlaid even in the case where observation is carried out from one direction when a writing or a coating is carried out. SOLUTION: The brilliant ink composition contains a hologram pigment constituted by flakes of a resin film having a metal reflection film; and a shearing viscosity-reduction imparting agent selected from pullulan, santhan gum, wellan gum, ramsan gum succinoglucan and dextran.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a glitter ink composition which can be suitably used for writing instruments, especially ballpoint pens.

[0002]

2. Description of the Related Art Heretofore, an ink composition using a metallic pigment such as gold or silver or a metallic pigment or a pearl pigment for obtaining a pearly handwriting has been provided. For example, Japanese Patent Laid-Open No. 7-
No. 118592 is a water-based ink composition using an aluminum pigment. Further, JP-A-8-151547 is an aqueous ink composition using a pearl pigment.

[0003]

However, in the case of the ink composition using such a conventional metal pigment, a handwriting or a coating having an effect (visual angle dependent polychromaticity: goniochromism) that makes the color look different depending on the viewing angle. I can't get a membrane. An ink composition using a pearl pigment also has a pearly luster, but almost no viewing angle-dependent polychromaticity can be confirmed. In particular, when the handwriting or coating film is observed from one direction, the light reflected by the particles scattered on the handwriting or coating film has different colors and brightness at each reflection point, and gives an ink that gives different brilliance to the handwriting or coating film. In particular, a glittering ink composition for writing such as a ballpoint pen has not been provided yet. On the other hand, in order to obtain an ink composition suitable for use in a writing instrument such as a ballpoint pen, regardless of whether it is water-based or oil-based, the dispersion stability of the pigment particles is good, and the sedimentation of the pigment particles can be prevented. It is important to make the ink excellent in storage stability.

The object of the present invention is to realize a plurality of reflection points having different colors and brightness when observed from one direction, which cannot be realized with conventional metal pigments and pearl pigments, and are scattered on the handwriting or coating film. An object of the present invention is to provide an ink composition capable of obtaining a handwriting or a coating film having a hologram property which simultaneously realizes viewing angle dependence and three-dimensional effect.

A further object of the present invention is that the dispersion stability of the pigments contained in the ink is good, the settling of the particles can be prevented, and the excellent storage stability is exhibited. An object is to provide an ink composition that can achieve the object.

[0006]

The present invention is a glitter ink composition containing a hologram pigment and a shear thinning agent.

The hologram pigment in the present invention is defined as a pigment whose pigment particles emit reflected light of the hologram and can give a handwriting or coating film a bright feeling of the hologram. For example, it is a pigment particle which diffracts and disperses incident light and gives hologram light by the interference action of the reflected light. The ink composition of the present invention containing this hologram pigment and a shear thinning agent is dotted with reflection points due to the hologram resin flakes in the handwriting or coating film in order to stabilize the dispersion without sedimentation of the hologram pigment particles. Since the reflection points have different colors and luminances, it is possible to realize a handwriting or a coating in which various hologram colors are scattered even when observed from one direction.

Further, since the ink composition of the present invention is an ink composition containing a shear thinning agent together with a hologram pigment, regardless of the type of aqueous or oily solvent,
In the case of the hologram pigment in the ink, particularly a hologram pigment composed of flakes of a hologram film having a metal reflection film, the hologram flakes have good dispersion stability and can prevent sedimentation of the particles. In addition, the ink can have excellent storage stability. That is, in the case of an ink composition containing a hologram pigment containing a metal element, depending on the type of the metal element, the specific gravity or particle size is larger than that of a pigment used for a normal felt-tip pen or ballpoint pen, but an ink containing such a hologram pigment. Even if it is a composition, if it is an ink composition containing a shear thinning imparting agent, it is possible to prevent sedimentation of the same particles, and it is possible to obtain an ink having excellent storage stability. As a result, the ink has great practicality as an ink for writing instruments such as a ballpoint pen and can be preferably used. Particularly, it is suitable when a hologram flake pigment is used.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION (Holographic Pigment) The hologram pigment of the present invention can be used as long as it has a hologram property and emits light having various colors and brightness even when observed from one direction. .

As the hologram pigment used in the present invention, for example, a master mold (mastering) in which a groove for holography is cut by laser light is prepared, and this master mold is used to emboss a thin film (resin film). A metal reflection film (metal film layer) is formed by processing, e.g., vapor-depositing a metal such as aluminum, and is cut into hologram pieces (flakes), or the surface thereof is further colored. Alternatively, a resin coated with an uncolored synthetic resin can be used. Further, a metal powder whose surface is subjected to hologram processing by embossing and then hardened by heat treatment or the like can be mentioned. Examples of the resin film (synthetic resin) to be the base material layer include polyethylene terephthalate and polyester. As the synthetic resin to be the base material layer, one kind or two or more kinds can be used. Further, as the metal to be formed into a film (formed into a film) by vapor deposition or the like on the base material layer,
Examples thereof include aluminum, gold, nickel, calcium, manganese, iron, copper and zinc. Further, the above-mentioned metals include metal compounds or alloys such as these oxides, and may also include components such as silicon or sulfur. Further, one kind or two or more kinds can be used as the metal, the metal compound or the alloy which is vapor-deposited on the base material layer.
The synthetic resin used for resin coating is not particularly limited, and examples thereof include epoxy resin, urethane resin, and acrylic resin. As the synthetic resin used for the resin coating, one kind or two or more kinds can be used. It is also possible to use a colored hologram coating by applying a colored resin coating using a solution in which a pigment or the like is dissolved in these synthetic resins. Further, as the hologram pigment, a pigment whose surface is treated with a surfactant, a general oil agent, a silicone oil, a fluorine compound, a silane coupling agent or the like can be used depending on the application.

The method for producing the hologram pigment is not particularly limited, but the following methods can be mentioned, for example. First, a synthetic resin film obtained by rolling a synthetic resin to be a base material layer is embossed with a laser beam. A metal is vacuum-deposited on the surface of the embossed synthetic resin film to obtain a hologram film. This is cut into particles having an appropriate shape (rectangle, square, circle, flat, etc.) and formed into particles, which are further immersed in a synthetic resin tank to coat the surface with a resin. The hologram pigment thus obtained has excellent heat resistance and solvent resistance, and exhibits excellent hologram properties.

As the hologram pigment of the present invention, a hologram flake of a resin film on which aluminum is vapor-deposited is used.
Technology Inc.) (Distributor: Silver Line) product name "Holographic Flake GP-142SV", "GP-14
2GD "," GP-142CU "," GP-142PW "," GP-142SV ",
"Same GP-144GD", "Same GP-144CU", "Same GP-144PW", "Same GP-14"
4SV ”can be exemplified. Further, "Diagram Hologram HG-S40EP", "Diagram HG-S20EP" manufactured by Diamond Industry Co., Ltd. can be exemplified. As the hologram pigment of the present invention, one kind or a mixture of two or more kinds can be used.

The major axis of the hologram pigment used in the present invention is not particularly limited, but is preferably 1.5 to 200 μm. The major axis of the flake hologram pigment is 1.5 μm
When it is less than 200 μm, the hologram color is inferior because the particles are too small, and when it exceeds 200 μm, when the ink is used for a writing instrument or applicator such as a ballpoint pen in which the particles need to pass through a narrow tube, it is necessary It is not preferable because it does not come out easily. The thickness of the hologram pigment is not limited, but is preferably 1 to 30 μm. The major axis or thickness of the pigment in the present invention means the maximum diameter or the maximum thickness of the particle surface of the flake (plate-like) pigment observed by an electron microscope (SEM).

The hologram pigment used in the ink composition of the present invention is preferably contained in an amount of 0.5 to 40.0% by weight based on the total amount of the ink composition.

(Solvent) 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 order to prevent the nib and the like from drying, a water-soluble organic solvent can be added to further delay the drying rate of water. 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. Lumonomethyl ether, dipropylene glycol monomethyl ether
Examples thereof include glycol ethers such as ter and dipropylene glycol monopropyl ether. These organic solvents may be used alone or in combination of two or more.

When the 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. To give an example of the organic solvent, aromatic hydrocarbons such as toluene and xylene, aliphatic hydrocarbons including alicyclic hydrocarbons and chain hydrocarbons such as methylcyclohexane, ethyl alcohol, isopropyl alcohol, benzyl alcohol, etc. Alcohols, methyl ethyl ketone, methyl isobutyl ketone, isophorone and other ketones, ethyl acetate, butyl acetate and other esters, ethyl cellosolve,
There are ether alcohols such as butyl cellosolve and propylene glycol monomethyl ether.

(Shear thinning agent) In the ink composition of the present invention, the viscosity of the ink is adjusted, the dispersion stability of the hologram pigment is ensured, and a good interference color is uniformly realized in a handwriting or a coating film. In addition, it is important to include a shear thinning agent together with the solvent so that the ink having excellent storage stability can be suitably used for a writing instrument such as a ballpoint pen. In particular, a hologram pigment having a metal reflection film has a larger specific gravity or particle size than pigment particles used in a normal felt-tip pen or ball-point pen, and therefore tends to settle. Therefore, in the present invention, it is extremely important to stabilize the dispersion and prevent the sedimentation of the ink containing the hologram pigment, and it is very effective to add a shear thinning agent.

From the above viewpoint, when water is used as the solvent, it is effective to use sugars. The "saccharide" in the present invention is defined as a general term for monosaccharides, oligosaccharides and polysaccharides, but for the above-mentioned purpose, it is preferable to adopt a component classified as a polysaccharide. For example,
Microbial polysaccharides and their derivatives 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, gati gum, arabinogalactan gum, arabic gum, quiche seed gum, pectin, starch, silice gum, pectin, carrageenan, alginic acid, agar, etc. Can be illustrated. In addition, water-soluble animal polysaccharides and their derivatives are used. For example, gelatin, casein, and albumin 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, pullulan, xanthan gum, welan gum, rhamsan gum, succinoglucan, an ink composition containing a microbial polysaccharide and derivatives thereof selected from dextran has a large specific gravity, even when containing a hologram pigment having a large particle size. The quasi-plastic flow property is excellent, the sedimentation-preventing effect of the holographic pigment, particularly the holographic pigment having a metal reflection film, is good over a long period of time, and the storage stability as an ink is excellent. The saccharides of the present invention can be used alone or in combination of two or more.

The saccharide content is 0.01-5.% In the total amount of the ink composition.
It is preferably contained in an amount of 0% by weight.

When an organic solvent is used as the solvent, it is preferable to use a non-pigment type gelling agent as the shear thinning agent. The non-pigmentary gelling agent referred to in the present invention is defined as a general term for pigments or substances that are not classified as extender pigments. An example of a non-pigment gelling agent is 2-
Metal soaps such as aluminum ethylhexanoate, sorbitol derivatives such as dibenzylidene sorbitol, alkylamides and fatty acid amides such as alkylglutamic acid alkylamides, oxidized polyethylene waxes, dextrin fatty acid esters, hydrogenated castor oil, 12-hydroxystearin There are acids, polyether / ester type surfactant gelling agents and the like, which can be appropriately used depending on the type of organic solvent.

The non-pigmentary gelling agent is preferably contained in the ink composition in an amount of 0.01 to 20.0% by weight. The above non-pigmented gelling agents may be used alone or in combination of two or more.

When an organic solvent is used as a solvent in the present invention, a particularly preferable embodiment is a case where a metal soap is used among the above-mentioned non-pigmentary gelling agents. This allows
A quick-drying ink composition in which the hologram pigment does not sediment can be obtained.

(Binder Resin) In the present invention, a binder resin can be used for the purpose of fixing the hologram pigment to the substance to be coated (base). The binder resin used in the present invention can be appropriately selected and used from the components of the resin miscible with the solvent. A water-soluble or water-dispersible resin is preferably used as the binder resin when water is used as the solvent. As an example, gum arabic, dextrin derivatives, cellulose derivatives such as carboxymethyl cellulose, polyvinyl alcohols, polyvinylpyrrolidones, polyacrylic acid and acrylic acid-based copolymers, and monomers such as maleic acid as a structural unit. A water-soluble natural or synthetic resin such as a resin containing can be preferably used. Further, unlike the above resins, an emulsion or a dispersion type resin, 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 particles to the base.

When the organic solvent is used as the solvent, an oil-soluble resin is preferably used as the binder resin. As an example, alicyclic, chain-containing aliphatic, aromatic petroleum hydrocarbon resin, vinyl acetate-based, vinyl copolymer resin such as terpene-based, polyvinyl acetal resin such as polyvinyl butyral, phenol-based, Formalin condensation resin such as xylene-based, vinyl acetate-based, terpene-based, etc., other, styrene-based resin, acrylic ester-based resin, polyamide resin, ketone resin, rosin, etc., synthetic, semi-synthetic,
Natural oil-soluble resins can be appropriately selected and used according to the type of organic solvent. Further, a non-aqueous emulsion can also be used.

The binder resin is preferably contained in the ink composition in an amount of 1.0 to 30.0% by weight. In addition, the binder resin described above may be of one type or of two types.
A mixture of two or more species can be used.

(Colorant) The colorant of the present invention can be used as long as it colors the handwriting or coating film, but it is preferable that it has solubility and dispersibility. For example, dyes and / or pigments can be preferably used.

The dye is selected according to the solvent and preferably has a sufficient solubility in the solvent. Specifically, when the solvent is water, acid dyes, direct dyes, water-soluble dyes such as basic dyes, and when the solvent is an organic solvent,
Oil-soluble dyes can be used. The pigment also preferably has sufficient dispersibility in the solvent. In particular,
Inorganic pigments, organic pigments, resin pigments, fluorescent pigments, metal pigments,
Bright pigments, colored emulsions and the like can be used. The colorant of the present invention can be used alone or in combination of two or more. Further, when the hiding property of the hologram pigment is not sufficient, the colorant is preferably a dark color. It is also possible to use a pigment or dye such as a metal pigment as a hologram light reflector together with a transparent hologram pigment having no metal reflection film. Also,
Depending on the background color of a base material such as paper or metal to be written or applied, a transparent hologram pigment having no metal reflection film may be blended alone.

The colorant of the present invention is preferably contained in the ink composition in an amount of 0.05 to 20.0% by weight.

(Other Additives) In the present invention, if necessary, a lubricant such as polyoxyethylene alkali metal salt, dicarboxylic acid amide, polyoxyethylene phosphate, N-oleyl sarcosine salt, Surfactants such as sorbitan monolaurate, rust inhibitors such as benzotriazole and tolyltriazole dicyclohexylammonium nitrate, antiseptic and fungicides such as benzoisothiazoline type, pentachlorophenol type and cresol can be added.

(Viscosity Range) The viscosity range of the ink composition of the present invention is not particularly limited, but is, for example, 500 to 10,0.
It can be carried out at 00 mPa · s. The viscosity is ELD
Type viscometer (3 ° R14 cone, rotation speed: 0.5 rpm,
20 ° C.).

(Form of Use of Ink Composition) The form of use of the present invention is not particularly limited, but as an example of a preferable form of use, the ink composition is contained in a tube such as metal or resin, and necessary. A form in which only the amount is squeezed from the tube to be used, a form in which a sponge or other ink absorber is impregnated in a cylindrical container and then stamped directly with the absorber, and ink is applied on one end of the ink containing tube. Examples include a mode in which parts are arranged and ink is applied with a pen tip.

A particularly preferred form is a so-called water-based gel ink ballpoint pen, which is most suitable for obtaining handwriting with the ballpoint pen of the ink composition of the present invention.

(Transparent Container) In any use form, the use of a transparent or translucent material for the ink container not only allows the ink remaining amount to be visually recognized from the outside,
The ink container looks like a different color depending on the viewing angle,
An effect can be obtained as if the container material itself has a hologram property. Furthermore, this enables high designability and innovative design. For example, it is desirable that the hologram pigment is contained in a component including a container and / or a cap, particularly in a resin molded product such as a transparent container.

[0035]

EXAMPLE Each component having the composition shown below was mixed and stirred to disperse it, and this was filtered and then defoamed to obtain an ink composition. Conventionally known methods were used for the dispersing method, the defoaming method, the filtering method, and the like.

That is, the product name "H
olographic Flake GP-142SV "(Spectratek Technology
Inc.) 7.0 parts by weight, Zansan gum (trade name "Kerzan", Sansei Co., Ltd.) as a shear thinning agent.
5 parts by weight, 0.4 parts by weight of 1,2-benzisothiazolin-3-one (trade name "Proxel XL2", manufactured by Avicia Co., Ltd.) as an antiseptic agent, 0.8 parts by weight of benzotriazole as a rust inhibitor, lubricant As a phosphoric acid ester-based surfactant (trade name "phosphanol PE510", manufactured by Toho Chemical Industry Co., Ltd.) 1.0 part by weight, 3.0 parts by weight of the following aqueous pigment dispersion as a colorant, and water-soluble as a solvent 5 parts by weight of glycerin as an organic solvent and 82.3 parts by weight of water were used.

(Aqueous Blue Pigment Dispersion) 25 parts by weight of phthalocyanine blue (CIPigment Blue 15: 3) was added to styrene-acrylic copolymer (trade name "John Cryl 68").
3 ", manufactured by Johnson Polymer Co., Ltd., weight average molecular weight 800
0): 5 parts by weight of sodium hydroxide was added and dissolved, and then dispersed by a ball mill to prepare a blue pigment dispersion having an average particle diameter of 0.06 μm and a solid content concentration of 30% by weight. .

(Preparation of Test Sample) A ballpoint pen tip made of stainless steel (ball material:
Silicon carbide) was filled in an ink containing portion made of a semi-transparent polypropylene hollow shaft connected in series at one end, and a ball-point pen of each test sample loaded with the ink containing portion was prepared.

When these ballpoint pens were used to write on commercially available high-quality paper and the visual effect of the handwriting was visually evaluated, it was found that the handwriting with the ink of the above-mentioned example had reflection points having different colors and brightness depending on the viewing angle. The holographic writing that was scattered around was realized. Further, when the ink filled in the ballpoint pen was observed, no sedimentation of hologram pigment particles was observed.

That is, the handwritings of the ink compositions of the examples exhibit excellent holographic properties having viewing angle dependence and three-dimensional effect, and reflection points having various colors and brightness are scattered in the handwritings. It is a handwriting. The storage stability was also good.

[0041]

The present invention is an ink composition containing a holographic pigment. Therefore, when written or applied using the ink composition,
The optical coloring of holograms that could not be realized with conventional metal pigments, pearl pigments and viewing angle-dependent polychromatic particles appears, and in particular, because the pigment particles are scattered in the handwriting or coating film, they have different colors and brightness. Reflection point (holographic brightness)
It is possible to obtain a handwriting or a coating film in which is scattered.

Further, since the ink composition of the present invention is an ink composition containing a shear thinning agent in addition to the above-mentioned pigment particles, good dispersion stability of the above-mentioned particles is secured and sedimentation of the particles is ensured. It is possible to prevent this, and it is possible to form a handwriting or a coating film having a hologram property while exhibiting excellent storage stability. Therefore, it can be suitably used for a writing instrument such as a ballpoint pen.

According to the ink of the present invention, since it is an ink composition containing, in addition to the above particles, a shear thinning agent, the above particles can be well dispersed and stabilized in the ink. The particles can be scattered on the handwriting or coating. Therefore, according to the ink of the present invention, depending on the viewing angle, a plurality of different colored interference colors transit to shine and shine, and even when observed from one direction, reflection points having different colors and brightness seem to be scattered. It is possible to employ a method for forming a handwriting that obtains a different handwriting or coating film.

Further, since this ink composition contains a shear thinning agent together with the above-mentioned particles, it can be contained in a transparent or translucent container to give a strong hologram brilliance in the appearance of the container itself. It is possible to obtain new design and novel design. For example, a transparent or semi-transparent ink containing portion is filled with ink containing a hologram pigment, and the ink containing portion is
A writing instrument such as a ballpoint pen that exhibits a hologram property can be adopted.

As described above, the ink composition containing the shear thinning agent can prevent the sedimentation of the holographic particles and maintain the quality such as writability for a long time.
The design of the ink container itself can be maintained for a long time.

The present invention is also applicable to stamp inks containing the above-mentioned various hologram pigments, stamps containing the stamp inks, watercolors such as poster colors containing the hologram pigments, and cosmetics such as nail polish. It is possible. Also, a plastic molded product in which the hologram pigment is contained in a resin molded product such as a writing instrument component such as a cap or a clip, or a cosmetic container can be used.

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 2C350 GA03 KC01 KF01 KF03 KF05                       NA19 NC05 NC20                 4J039 AB01 AB07 AB08 AD03 AD06                       AD08 AD09 AD18 AE02 AE08                       BC59 BE01 BE02 BE12 BE23                       CA03 CA04 CA06 CA07 EA21                       EA33 EA48 GA12 GA26 GA27

Claims (16)

[Claims] 1. A glittering ink composition containing a hologram pigment and a shear thinning agent. 2. The glitter ink composition according to claim 1, wherein the hologram pigment is composed of flakes of a hologram film having a metal reflection film. 3. The glitter ink composition according to claim 1, wherein the holographic pigment has a resin film with a colored or uncolored resin coating on the surface of the flake. 4. The major axis of the hologram pigment is 1.5 to 2
The glitter ink composition according to claim 1, which has a thickness of 00 μm and a thickness of 1 to 30 μm. 5. The glitter ink composition according to claim 1, wherein the shear thinning agent is a saccharide and water is contained as a solvent. 6. The glitter ink composition according to claim 5, wherein the saccharide is a microbial polysaccharide and a derivative thereof selected from pullulan, xanthan gum, welan gum, rhamsan gum, succinoglucan and dextran. 7. The glitter ink composition according to claim 1, wherein the shear thinning agent is a non-pigmented gelling agent and an organic solvent is contained as a solvent. 8. The glitter ink composition according to claim 7, wherein the non-pigmentary gelling agent is a metal soap. 9. The glitter ink composition according to claim 1, further comprising a binder resin. 10. The glitter ink composition according to claim 1, further comprising a colorant. 11. A writing instrument containing the glitter ink according to any one of claims 1 to 10. 12. A writing instrument in which the glitter ink according to any one of claims 1 to 10 is contained in a transparent or translucent container. 13. A writing instrument in which a hologram pigment is contained in a resin molded body of a component including a container and / or a cap. 14. A method for forming a handwriting in which hologram pigments are scattered in the handwriting and each reflection point of the hologram pigment particles having different colors and brightness is formed in the handwriting. 15. A hologram pigment is scattered between colorant particles contained in an ink, and each reflection point by the hologram pigment particles having different colors and brightness is written with a hue of the colorant as a background color. The method of forming the formed handwriting. 16. A hologram pigment is scattered with a colorant contained in the ink as a background color, and each reflection point by the hologram pigment particles having different colors and brightness is written with the hue of the colorant as the background color. Method of forming handwriting formed on the.