JP2001214095A - Water-based ink composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a water-based ink composition having a sufficient luminous function by the illumination of near ultraviolet to ultraviolet rays in the water- based ink component used by filling a writing tool or a coating tool such as a marking pen, a brush-pencil and a ball-point pen with the composition. SOLUTION: This water-base ink composition at least containing a coloring matter, water and a water-soluble solvent is characterized in that the coloring matter is colorless or white at least in daylight, and contains a fluorescent material emitting a clear chromatic color by absorbing the near ultraviolet to ultraviolet rays.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a marking pen,
The present invention relates to a water-based ink composition having a light-emitting function for use in writing implements such as brush pens and ball-point pens, and printing inks.

[0002]

2. Description of the Related Art Conventionally, it has been known to use an organic daylight fluorescent pigment as a coloring material. For example, Japanese Unexamined Patent Application Publication No.
No. 1 discloses water, a water-soluble organic solvent, a fluorescent color pigment (0.
An aqueous dispersion of polymer particles of 1 to 1.0 μm dyed with an organic daylight dye) and a thickening agent are disclosed. The organic daylight fluorescent pigment has colored reflected light under daylight, absorbs near-ultraviolet to ultraviolet light in daylight, and emits light having a wavelength equal to or near the reflected light (ie, fluorescence). Colorant. Since the wavelength of the reflected light is equal to or close to the wavelength of the fluorescent light, the organic daylight fluorescent pigment produces a very clear color. That is, in the reflected light in the wavelength region that is visually perceived as a color, the color developed only by normal reflection has a reflectance of 100% with respect to the light source light.
Fluorescence is added and reflected light is 100%
The color is very sharply developed by the mechanism described above. As the organic daylight fluorescent pigment, a colorant in which an aqueous dispersion of polymer fine particles such as the above colorant is first deposited with an organic daylight fluorescent dye, for example, NKW2102, 2104 and 2107 (manufactured by Nippon Fluorescent Co., Ltd.) and the like is there. Further, pigment-dye types and plastic-dye types are also known. Lumogen L Y
yellow, Lumogen Yellow Ora
nge, Lumogen L Red Orange
(BASF, Germany) is known. The plastic powder type is obtained by dyeing daylight fluorescent dye on plastic particles, and the plastic particles include melamine, toluenesulfonamide formaldehyde resin,
Benzoguanamine formaldehyde resin, polyacrylic copolymer, polyvinyl chloride and the like are known, and as daylight fluorescent dyes, rhodamine B, rhodamine 6G, azosol brilliant yellow 6G and the like are known. In recent years, in order to enhance handwriting of an aqueous ink composition using an organic daylight fluorescent pigment as a coloring material, near ultraviolet light has been used for illumination.

[0003]

However, in order to make fluorescent color more conspicuous, in order to irradiate near ultraviolet mainly in a dark place,
Among the colors of the organic daylight fluorescent pigments, the reflected light of daylight disappears, resulting in a slightly perceptible unclear handwriting, which is not satisfactory in a dark place.

That is, the present invention provides an aqueous ink composition having a colorless or white handwriting or a chromatic handwriting in daylight having a sufficient light-emitting function for near-ultraviolet to ultraviolet light illumination in a dark place. The task is to provide.

[0005]

According to the present invention, there is provided an aqueous ink composition containing at least a coloring material, water and a water-soluble organic solvent, wherein the coloring material is colorless or white under daylight, and is near ultraviolet to ultraviolet. The gist of the present invention is a water-based ink composition containing at least a fluorescent substance that emits a clear chromatic color by absorbing light.

Hereinafter, the present invention will be described in detail. The coloring material used in the aqueous ink composition of the present invention is a fluorescent substance which is colorless or white at least under daylight and absorbs near-ultraviolet to ultraviolet light to emit a clear chromatic color. This fluorescent substance is exposed to black light in a dark place,
It is used for the purpose of giving clear chromatic light emission and giving a handwriting that emits clear fluorescent light.

[0007] Fluorescence in the present invention refers to light emission that absorbs near-ultraviolet light to ultraviolet light and emits visible light when stimulated by the energy. The fluorescent substance of the present invention emits strong chromatic visible light when irradiated with a black light lamp. Further, they are colorless or white under daylight, and stop emitting light as soon as irradiation of near-ultraviolet to ultraviolet light stops. Incidentally, a black light lamp is a device that blocks a visible part from a mercury ray emitted from a low-pressure mercury lamp with a filter, and is generally 254 nm or 365 nm.
It is a kind of fluorescent discharge tube that emits near-ultraviolet light having a wavelength of nm. Phosphors which are colorless or white under daylight and emit strongly chromatic visible light upon irradiation with near-ultraviolet to ultraviolet light include, for example, MnCl ₂ , Sm ₂ (SO ₄ ) ₃ .8H ₂ O,
_{Eu 2 (SO 4) 3 ·} 8H 2 O, CaWO 4, CaMo 4, B
aPt (CN) ₄ , NaCl: Mn, KCl: Tl, Z
_{n 2 SiO 4: Mn, 6MgO} · AsO 5: there is Mn, and the like. As a commercially available product, for example, LUMIUX EFFE
CT PIGMENT Blue A, Blue
OL, Green A, Green OL, Yellow-orange A, Red A,
Blue-green O, White-ye
green-yellow O (above, manufactured by Riedel de Han (Germany)). The amount used is preferably from 1 to 20% by weight. If the amount used is less than 1% by weight, the fluorescent function may not be sufficiently satisfied. In addition, when the viscosity is high, ink follow-up properties may be poor, and ink ejection may be poor.

In addition, commonly used coloring materials can be used in combination. For example, water-soluble dyes such as acid dyes, basic dyes, and direct dyes; organic pigments such as phthalocyanine blue, monoazo yellow, titanium oxide, and aluminum paste; inorganic pigments; metal powder pigments;
Species or two or more of them can be used in combination.

Water is used as the main solvent.

The water-soluble organic solvent is used for the purpose of preventing the ink from drying at the pen tip and preventing the ink from freezing at low temperatures. Specifically, glycols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, polyethylene glycol, 1,3-butylene glycol, thiodiethylene glycol, 1,5-pentanediol, and glycerin; Monomethyl ether, diethylene glycol monomethyl ether, 2-pyrrolidone, N-methyl-2-pyrrolidone, triethanolamine and the like can be used alone or in combination.

In addition to the above components, various additives conventionally used in aqueous ink compositions can be used. For example, a resin can be used to fix a solid in the aqueous ink composition to a writing surface such as paper. Specifically, ammonium salt of acrylic resin, styrene-
Examples include ammonium salts of acrylic copolymers, ammonium salts of styrene-maleic acid resins, water-insoluble resins such as acrylic resins, vinyl acetate resins, styrene-acrylic copolymers, and styrene-butadiene copolymers. . The water-insoluble resin is used in the form of an aqueous emulsion.

Further, a dispersing agent can be used for preventing the fluorescent substance and the pigment used in the aqueous glossy ink composition of the present invention from solidifying over time. Examples thereof include known nonionic and anionic surfactants, polyolefin emulsions, fatty acid esters of polyoxyethylene diglycerin borate, and polyoxyethylene alkylamine fatty acid amides. Also, humectants such as urea, ethylene urea and thiourea, and N-fatty acid acyl-L-
Glutamates, lubricants such as N-acyl amino acid salts,
Various additives such as benzothiazoline-based and omazine-based preservatives, benzotriazole and other rust inhibitors, and antifoaming agents can be used.

In addition, the viscosity of the ink composition is about 1000
When it is lower than 0 mPa · s, it is necessary to stir and redisperse before use, so a writing instrument having a built-in stirrer is used. Further, the viscosity of the ink composition is about 10,000 mPa.
In the case of s or more, there is no need to redisperse, so a writing implement having a raw ink structure is used. Incidentally, the reason for the necessity of redispersion arises from the fact that the specific gravity and the particle size of the fluorescent substance are larger than those of the coloring materials generally used for aqueous inks. That is,
The fluorescent substance is easily separated in the ink and is divided into a supernatant and a solid containing the fluorescent substance. Therefore, unless an external force such as shaking is applied immediately before use, the concentration of the fluorescent substance in the ink will not be uniform, and handwriting with a uniform concentration cannot be obtained. Therefore, a viscosity modifier can be used for the purpose of increasing the ink viscosity. For example, natural polymers such as guar gum and derivatives thereof, xanthan gum, locust bean gum, welan gum, ramzan gum, tragacanth gum, sodium carboxymethyl cellulose, hydroxypropyl cellulose, and cellulose polymers such as hydroxypropylmethyl cellulose, and polyvinylpyrrolidone can be used. .

In producing the ink of the present invention, various conventionally known methods can be employed. For example, it can be easily obtained by blending the above respective components and stirring and mixing with a stirrer such as a homogenizer or a Henschel mixer.

[0015]

The handwriting of the water-based ink composition according to the present invention is illuminated by a black lamp that emits near-ultraviolet light in a dark place and emits strong visible light (clear chromatic color). Handwriting with a different color tone.

[0016]

EXAMPLES Example 1 Colorant (fluorescent substance, LUMIUX EFFECT PIGMENT Red A, manufactured by Riedel De Han) 10.0 parts by weight Propylene glycol 10.0 parts by weight Water 59.8 parts by weight Dispersant (HYTEC E) -1000, polyolefin emulsion, manufactured by Toho Kagaku Co., Ltd. 10.0 parts by weight Fungicide (Proxel GXL, 1,2-benzisothiazolin-3-one, manufactured by IC Japan KK) 0.2 parts by weight Fixing resin (John Krill J61J, ammonium salt of styrene-acrylic acid copolymer, manufactured by Johnson Polymer Co., Ltd.) 10.0 parts by weight After the above components were subjected to dispersion treatment with a homogenizer for 10 minutes,
A colorless to slightly cloudy ink was obtained.

Example 2 Coloring material (fluorescent substance, LUMIUX EFFECT PIGMENT Red A, manufactured by Riedel de Han) 10.0 parts by weight Propylene glycol 10.0 parts by weight Glycerin 5.0 parts by weight Water 63.8 parts by weight 0.2 parts by weight of fungicide (Proxel GXL, 1,2-benzisothiazolin-3-one, manufactured by IC Japan Co., Ltd.) Dispersant / fixing resin (Johncryl J61J, ammonium salt of styrene-acrylic acid copolymer) , Johnson Polymer Co., Ltd.) 10.0 parts by weight Thickener (xanthan gum, manufactured by Sanseki Co., Ltd.) 1.0 part by weight Xanthan gum is removed from the above components, and after dispersion treatment with a homogenizer for 5 minutes, xanthan gum is added. In addition, the mixture was stirred with a three-one motor for 2 hours to obtain a colorless to slightly cloudy ink.

Example 3 Coloring material 1 (Alpaste WXM0630, 60% by weight of aluminum powder, manufactured by Toyo Aluminum Co., Ltd.) 5.0 parts by weight Coloring material 2 (fluorescent substance, LUMIUX EFFECT PIGMENT Blue LED, Riedel de) 5.0 parts by weight Dispersant (EN-120A, fatty acid ester of polyoxyethylene diglycerin borate, manufactured by Toho Chemical Co., Ltd.) 2.0 parts by weight Fixing resin (John Krill 450, styrene) -Emulsion of acrylic acid copolymer, manufactured by Johnson Polymer Co., Ltd. 10.0 parts by weight Water 65.4 parts by weight Ethylene glycol 7.5 parts by weight Fungicides (Proxel GXL, 1,2-benzoisothiazoline- 3-one, manufactured by ICI Japan Co., Ltd.) 0.2 parts by weight Thickener (xanthan gum, manufactured by Sansei Co., Ltd.) 0.9 parts by weight In the above components, xanthan gum was removed, and after dispersion treatment with a homogenizer for 5 minutes, xanthan gum was added and stirred with a three-one motor for 2 hours to obtain a silver ink.

Example 4 Colorant 1 (Alpaste WXM0630, 55% by weight of aluminum powder, manufactured by Toyo Aluminum Co., Ltd.) 10.0 parts by weight Colorant 2 (fluorescent substance, LUMIUX EFFECT PIGMENT Green A, Riedel de) 15.0 parts by weight Dispersant (EN-120A, as described above) 4.0 parts by weight Fixing resin (Movinyl DM772, acrylic copolymer resin emulsion, manufactured by Hoechst Gosei Co., Ltd.) 10.0 parts by weight Water 50.6 parts by weight Antifoaming agent (TSA772, emulsion of silicone oil, manufactured by Toshiba Silicone Co., Ltd.) 0.2 parts by weight Ethylene glycol 9.0 parts by weight Viscosity modifier (polyvinyl pyrrolidone K-15, manufactured by BASF) 1.0 parts by weight Preservative (Proxel GXL, as described above) 0.2 parts by weight Dispersing treatment for 5 minutes to obtain a silver ink.

Example 5 Colorant 1 (NKW2107, organic daylight fluorescent colorant, manufactured by Nippon Fluorescent Co., Ltd.) 12.0 parts by weight Colorant 2 (LUMIUX EFFECT PIGMENT Red A, fluorescent substance, described above) 8.0 Parts by weight Dispersant / fixing resin (John Krill J62, manufactured by Johnson Polymer Co.) 10.0 parts by weight Water 55.8 parts by weight Propylene glycol 8.0 parts by weight Glycerin 5.0 parts by weight Preservative (Proxel GXL, as described above) 0.2 parts by weight Thickener (Locust Bean Gum, manufactured by Sanseki Co., Ltd.) 1.0 part by weight Excluding locust bean gum in the above ingredients, dispersing with a homogenizer for 5 minutes, and then adding locust bean gum. The mixture was stirred with a three-one motor for 2 hours to obtain an ink having a pink color.

COMPARATIVE EXAMPLE 1 The fluorescent substance LUMILUX EF which is the coloring material of Example 1
Instead of FECT PIGMENT RedA, Lu
A fluorescent yellow ink was obtained in the same manner except that mogen L Yellow was added.

Comparative Example 2 LUMILUX EFFECT PIGME of Example 5
Pink ink was obtained in the same manner except that water was added except for NT Red A.

As described above, the aqueous ink compositions obtained in Examples 1 and 4 and Comparative Example 1 were applied to a commercially available rear end knock type brush structure as a writing tool with a built-in ink (modified brush, product code: ZL9B, Pentel Co., Ltd.) ), And writing was performed on high-quality paper. The handwriting was illuminated with black light in a dark place, and the light emission state of the handwriting was visually checked. The aqueous ink compositions obtained in Examples 2, 3, and 5 and Comparative Example 2 were prepared by using a ball-point pen tip (material: stainless steel) using a 0.8 mm-diameter ball (material: superhard) in a polypropylene cylinder. 0.8 g is filled in the cylinder of the ballpoint pen fitted in one end, and 0.1 g of the ink backflow preventer is filled in one end of the cylinder to make a ballpoint pen refill. It was placed in a cylinder and written, and the handwriting was illuminated with black light in a dark place, and the light emission state of the handwriting was visually checked.
Table 1 shows the results.

[0024]

[Table 1]

[0025]

As described above in detail, the aqueous ink composition according to the present invention has an excellent function of emitting light in a dark place different from handwriting under daylight by adding a fluorescent substance. Ink composition.

Claims (2)

[Claims] 1. A water-based ink composition containing at least a coloring material, water and a water-soluble organic solvent, wherein the coloring material is colorless or white under daylight, and absorbs near-ultraviolet to ultraviolet light to provide a sharp color. An aqueous ink composition comprising at least a fluorescent substance that emits colored light. 2. The aqueous ink composition according to claim 1, wherein the coloring material further contains aluminum powder.