JP2003020434A - Ink composition and ball-point pen using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an ink composition having excellent stability of ink with the lapse of time. SOLUTION: This composition comprises at least a pigment obtained by coating a part or the whole of metal fine particle with a colorless or colored resin having transparency, a liquid medium and a tertiary amine.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ink composition having good stability over time, and a ball as a writing member and a tip of the ball protruding as a pen tip for forming a handwriting using the ink. The present invention relates to a ballpoint pen that uses a ballpoint pen tip consisting of a ball holder that is held by a user.

[0002]

2. Description of the Related Art Conventionally, an ink composition containing a pH stabilizer or a pH adjusting agent to adjust the pH of the ink composition is disclosed in JP-A No. 11-349885. Is disclosed in.

The invention described in JP-A No. 11-302587 contains a metal powder pigment, a pigment, an anionic polymer, a thickener and a pH stabilizer, and the pH of the ink composition is 8.0.
A water-based metallic ink composition which is adjusted to 10 to suppress a change in viscosity due to aggregation and precipitation of anionic polymer is described.

[0004]

However, the above-mentioned conventional techniques still have technical problems regarding the reactivity between the pH adjusting agent and the ink components. That is, when a metal pigment or a pigment partially or wholly coated with a resin is used, the metal pigment (particularly aluminum) and the acid component or ions eluted or liberated from the resin layer coating the metal pigment form an ink When the pH is lowered and the dispersion of the components in the ink (for example, the dispersion of the pigment used as the colorant or the emulsion of the water-insoluble resin used as the fixing agent) is broken, the ink components are aggregated or precipitated, and In some cases, the flow of ink in the fine ink passages may be obstructed, and in some cases, a portion of the handwriting surface where ink does not flow, such as strokes or scratches, is formed on the handwriting. As a result, if it is remarkable, it will be impossible to write. Therefore, in order to suppress the decrease in the ink pH, it may be possible to adjust the pH with a basic component such as caustic soda. However, if an acid component or ion elutes with time from the resin layer coating the metal pigment. However, there is a problem in that a substance insoluble in the ink solvent is generated by reacting with the basic component, and eventually the ink is clogged with the pen tip to cause strokes and scratches in the handwriting. In particular, when this resin layer uses urea resin, phenol resin or their derivatives or modified products, unreacted formaldehyde and its derivatives remain in the resin layer and formaldehyde elutes over time. Then, it reacts with the basic component to form a substance insoluble in the ink solvent, which causes the same problem as described above.

An object of the present invention is to provide an ink composition in which the stability of the ink with time is good, and further to obtain a ballpoint pen free from line skipping and smearing (a phenomenon in which part of handwriting is cut).

[0006]

That is, according to the present invention, a part or whole of metal fine particles is coated with a transparent colorless or colored resin, a liquid medium and a tertiary amine. The gist is at least the ink composition.

The present invention will be described in detail below. The tertiary amine used in the ink composition of the present invention is a tertiary amine even if the metal foil powder or the component contained in the resin layer coating the metal foil powder is ionized or liberated due to long-term storage of the ink. Since the reaction with the ionized or liberated components of the resin layer produces a substance soluble in the ink solvent, it does not produce a substance that causes clogging that may cause handwriting jumps or scratches. In particular, triethanolamine is easily soluble in the ink solvent, has a high boiling point and is hard to volatilize, does not evaporate from the pen tip, etc., and the pH change of the ink is small, so that it can be suitably used. The amount of these tertiary amines used is not particularly limited, and can be appropriately selected depending on the types of other components, the amounts used, and the pH of the target ink. More specifically, the amount of the tertiary amine used is p when adjusting the ink.
The amount of H is, for example, about 8.0 to 9.0.

The metal foil powder coated with a transparent colorless or colored resin layer used in the ink composition of the present invention is a coloring agent that gives a feeling of brightness of a plurality of colors in handwriting. Commercially available, Elgi Silver #
325, Red Gold # 325, and Blu
e Gold # 325, Red # 325, and B
lue # 325, the same Green # 325, the same V
iolet # 325, Black # 325, Copper # 325 (particle size: 44 μm or more), ERGI Silver # 500, Gold # 50
0 (above grain size 28 μm), and Elgi # 10
There are 0 series (particle size 150 μm), LG # 150 series (particle size 105 μm), and LG # 200 series (particle size 74 μm) (all manufactured by Oike Kogyo Co., Ltd.). The metal foil powder may be used alone or in combination of two or more kinds.

The amount of the metal foil powder coated with the transparent colorless or colored resin layer used in the present invention is 0.5 to 15% by weight, preferably 1. It can be used in the range of 0 to 8.0% by weight.

Further, the size of the metal foil powder coated with the transparent colorless or colored resin layer used preferably has a particle diameter of 150 μm or less. Particle size is 170 μm
This is because if it is larger, the pen tip may become clogged with ink and writing may not be possible.

As a nib for discharging a metal foil powder coated with such a transparent colorless or colored resin layer to form a handwriting, there is a marker using a fiber bundle, a valve type applicator, or the like. Although it can be illustrated, a ballpoint pen having a ballpoint pen tip that holds a ball as a writing member partially protruding and held at the tip can be preferably used. In particular, the ball, which is a writing member that transfers ink to the recording surface by rotation, is a sintered body of silicon carbide, and the holes formed on the surface have a depth of 0.3 μm or more and 1.0 μm or less, and an average hole diameter. 1μm or 10μm or less, the ball is preferred average distribution number of holes on the ball is three or / 50μcm ² below 1 / 50μcm ² or more. By using such a ball, even if it is a metal foil powder coated with a transparent colorless or colored resin layer having a particle size as described above, the ink can ride on the ball well and a part of the handwriting It is possible to continuously form good handwriting without breaking the stroke.

It is also possible to use a part or all of the metal fine particles in combination with a pigment coated with a transparent colorless or colored resin to use other colorants. From the ink obtained by the combined use, it is possible to obtain handwriting having a contrast due to the color tone originally possessed by the metal pigment colored chromatically by coating with a colored resin and the color tone of the other colorant used in combination. As the colorant that can be used in combination, pigments and dyes conventionally used in water-based ink compositions can be used without limitation. Specific examples of pigments include carbon blacks such as Farnest black, contact black, thermal black, and acetylene black, black iron oxide, yellow iron oxide, red iron oxide, ultramarine blue, navy blue, cobalt blue, titanium yellow, turquoise, molybdate orange. Inorganic pigments such as titanium oxide, C.I. I. PIGMENT RE
D2, ibid 3, ibid 5, ibid 17, ibid 22, ibid 38, ibid 41,
Ibid 48: 2, ibid 48: 3, ibid 49, ibid 50: 1, ibid 5
3: 1, 57: 1, 58: 2, 60, 63:
1, the same 63: 2, the same 64: 1, the same 88, the same 112, the same 1
22, Same 123, Same 144, Same 146, Same 149, Same 1
66, 168, 170, 176, 177, 1
78, 179, 180, 185, 190, 1
94 the same 206, the same 207, the same 209, the same 216, the same 24
5, C.I. I. PIGMENT ORANGE 5 and 1
0, ibid 13, ibid 16, ibid 36, ibid 40, ibid 43, C.I.
I. PIGMENT VIOLET 19, ibid 23, ibid 31, ibid 33, ibid 36, ibid 38, ibid 50, C.I. I. PI
GMENTBLUE 2, Same 15, Same 15: 1, Same 1
5: 2, 15: 3, 15: 4, 15: 5, 1
6, the same 17, the same 22, the same 25, the same 60, the same 66, C.I.
I. PIGMENT BROWN 25, 26, C.I.
I. PIGMENT YELLOW 1, 3, 3, 12,
Ibid 13, ibid 24, ibid 93, ibid 94, ibid 95, ibid 97, ibid 99, ibid 108, ibid 109, ibid 110, ibid 117, ibid 1
20, ibid 139, ibid 153, ibid 166, ibid 167, ibid 1
73C. I. PIGMENT GREEN 7 and 1
0, 36 and the like. These may be used alone or in combination of two or more.

Further, since it is advantageous in producing a pigment ink,
It is also possible to use an aqueous ink composition base of a dispersed pigment in which the pigment is dispersed in an aqueous medium. As a specific example, Ryu
dye-W series (Dainippon Ink and Chemicals, Inc.)
Made), Sandye Super series, Emaco
l series (above, Sanyo Pigment Co., Ltd.), EM Co
lor series, Rio, Fast series (all manufactured by Toyo Ink Mfg. Co., Ltd.), Fuji SP series (manufactured by Fuji Pigment Co., Ltd.), MicroPigmo series, MicroJet series (all manufactured by Orient Chemical Co., Ltd.) Organic pigment dispersions, NKW series (Nippon Fluorescent Chemicals Co., Ltd.), Cosmocolor series (Toyo Soda Co., Ltd.), Shinrohi color base series (Shinrohi Co., Ltd.), etc. Can be mentioned. These may be used alone or in combination of two or more.

As the dye, conventionally known water-soluble dyes such as acid dyes, basic dyes and direct dyes can be used. Acid dyes include C.I. I. Acid
Black 1, same 2, same 24, same 26, same 31, same 52, same 107, same 109, same 110, same 119, same 1
54, C.I. I. Acid Yellow 1, ibid 7, ibid 17, ibid 19, ibid 23, ibid 25, ibid 29, ibid 38, ibid 4
2, 49, 61, 72, 78, 110, 1
27, 135, 141, 142, C.I. I. Aci
d Red 8, ibid 9, ibid 14, ibid 18, ibid 26, ibid 2
7, 35, 37, 51, 52, 57, 8
2, ibid 83, ibid 87, ibid 92, ibid 94, ibid 111, ibid 1
29, 131, 138, 186, 249, 2
54, 265, 276, C.I. I. AcidViol
et 15, ibid 17, ibid 49, C.I. I. Acid Bl
ue 1, same 7, same 9, same 15, same 22, same 23, same 2
5, Same 40, Same 41, Same 43, Same 62, Same 78, Same 8
3, 90, 93, 100, 103, 104,
112, 113, 158, C.I. I. Acid G
reen 3, ibid 9, ibid 16, ibid 25, ibid 27, C.I.
I. Acid Orange 56, a basic dye includes C.I. I. Basic Yellow 11, C.I.
I. Basic Orange 21, C.I. I. Basi
c Red 1, 13 and C.I. I. Basic Vi
olet 3C. I. Basic Blue 1, the same
7, C.I. I. Basic Green 1, C.I. I. B
asic Black 2 and 8, as direct dyes, C.I. I. Direct Black 17 and 1
9, the same 22, the same 32, the same 38, the same 51, the same 71, C.I.
I. Direct Yellow 4, the same 26, the same 4
4, 50, C.I. I. Direct Red 1, 4, 3, 23, 31, 37, 39, 75, 8
0, 81, 83, 225, 226, 227,
C. I. Direct Blue 1, 15 and 4
1, the same 71, the same 86, the same 87, the same 106, the same 108, the same 199 and the like. In addition, C.I. I. Food dyes such as Food Yellow 3 and Malachite Green (C.I. 420
00), Victoria Blue FB (C.I. 4404)
5), methyl violet FN (C.I.
5), Rhodamine F4G (CI.45160), Rhodamine 6GCP (CI.45160) can also be used.
The above pigments, disperse pigments and dyes can be mixed and used. The amount of the colorant used in the present invention is preferably equal to or less than the amount of the metal foil powder.

The thickening agent is used to prevent sedimentation of the metal foil powder coated with a transparent colorless or colored resin and to obtain appropriate viscosity physical properties as an ink for ballpoint pens. Specific examples include seed polysaccharide guar gum,
Locust bean gum and its derivatives, microbial xanthan gum, welan gum, rhamsan gum, succinoglucan, Alcaligenes latus B-1
B-16 polymer (alka gum) which is an acidic polysaccharide produced by 6 strains of bacteria, seaweed polysaccharide carrageenan, alginic acid and its derivatives, resin polysaccharide tarragant gum, cellulosic sodium carboxymethyl cellulose, hydroxypropyl cellulose and the like are used. it can. In particular, polysaccharides have relatively stable physical properties even after long-term storage or when the pH changes over time, and because the viscosity of the polysaccharide is greatly reduced by the rotation of the ball during writing, it has excellent writing characteristics as a ballpoint pen.

The thickeners may be used alone or in combination of two or more. The amount of the thickener used is, especially when used for a ballpoint pen, 0.05 to 5.0 with respect to the total amount of the ink composition.
%, Preferably 0.1 to 1.0% by weight. 0.
If it is less than 05% by weight, the metal foil powder may settle. Further, when a pigment is used as the colorant, the effect on the sedimentation of the pigment may be reduced. On the other hand, 5.0
When the content exceeds the weight%, the viscosity of the ink composition becomes too high, and the ejection amount of the ink from the pen tip portion may deteriorate.

Water can be used as the main solvent of the liquid medium for making the ink. Further, conventionally known for various qualities as an ink, for example, for the purpose of preventing ink from freezing at low temperature, preventing ink from drying with a pen tip, dispersing medium of pigment, dissolving agent of dye, dissolving / dispersing of viscosity adjusting agent, etc. It is possible to use the water-soluble organic solvent. Specific examples of the water-soluble organic solvent include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, polyethylene glycol, hexylene glycol, 1,3-butylene glycol, thiodiethylene glycol, 1,5-
Glycols such as pentanediol and glycerin, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol monoethyl ether, dipropylene glycol Examples thereof include glycol ethers such as monoethyl ether, 2-pyrrolidone and N-methyl-2-pyrrolidone. These water-soluble organic solvents can be used alone or in combination. The amount used is preferably 10 to 60% by weight based on the total amount of the ink composition.

A solid material in an ink such as a metal pigment or a colorant coated with a transparent or colorless resin which is soluble or dispersible in a liquid medium used as a fixing agent is used for a paper or the like. It can be used for fixing to the writing surface. Specific examples include alkali metal salts of styrene-acrylic copolymers, amine salts, ammonium salts, alkali metal salts of α-methylstyrene-acrylic acid copolymers, amine salts, ammonium salts, styrene-acrylic ester-acrylic copolymers. Water-soluble resins such as alkali metal salts, amine salts, and ammonium salts of polymers, acrylic resins, vinyl acetate resins, water-insoluble resins such as styrene-butadiene copolymers, and the like, including modified products of the above resins. Be done. The water-insoluble resin is used in the form of an aqueous emulsion.

In addition, wetting agents and lubricants such as urea, ethylene urea and thiourea, antiseptics such as benzothiazoline and omadine, rust preventives such as benzotriazole, and natural polymers as dispersion stabilizers for pigments. Resins such as synthetic polymers, polyoxyethylene alkyl ethers, polyoxyethylene phenyl ethers, polyoxyethylene oleyl ethers, surfactants such as polyoxyethylene octyl phenyl ether and its sulfates, defoaming agents such as silicone emulsions, etc. Various additives can be used.

In producing the ink of the present invention, various conventionally known methods can be adopted. For example, each component (metal foil powder coated with a transparent colorless or colored resin, a colorant, a thickener, water, a water-soluble organic solvent,
It is easily obtained by blending additives) and stirring and mixing with a stirrer such as a turbo mixer or a Henschel mixer. More specifically, for example, a dispersion pigment, water, a water-soluble organic solvent, and a metal pigment coated with a transparent colorless or colored resin are mixed to prepare a metal pigment dispersion, An ink can be prepared by adding a thickener, a pH adjuster, an additive and the like. In addition, as a method of dispersing, defoaming, filtering, etc., which is performed when preparing the ink,
Conventional methods can be adopted.

[0021]

[Function] The tertiary amine represented by triethanolamine does not have hydrogen in the molecule which easily becomes a hydrogen ion, and the tertiary amine and the acid component contained in the metal pigment or the coating resin layer are included. Since the reaction product with the ion liberated from the or its derivative does not form an aggregate and is soluble in the ink solvent, it does not cause clogging at the pen tip.

[0022]

The present invention will be described in more detail based on the following examples and comparative examples, but the present invention is not limited to these examples. Example 1 LJ Green # 325 (crushed fine pieces of green metal vapor deposition foil, Oike Industry Co., Ltd., particle size 44 μm) 4.0 parts by weight Sandy Super Blue 1808 (blue colorant, Sanyo Dye Co., Ltd.) 2.0 parts by weight John Cryl 1535 (resin, styrene-acrylic copolymer, manufactured by Johnson Polymer Co., Ltd.) 10.0 parts by weight NP-10 (dispersant, polyoxyethylene (10) nonylphenyl ether, Nikko Chemicals ( Co., Ltd.) 1.0 parts by weight water 64.2 parts by weight ethylene glycol 10.0 parts by weight glycerin 7.0 parts by weight Proxel GXL (preservative, 1,2-benzisothiazolin-3-one, ICI Japan Co., Ltd.) 0.2 parts by weight TSA739 (antifoaming agent, silicone emulsion, GE Toshiba Silicones Co., Ltd.) 0.2 parts by weight Xanthan gum 0.9 60 minutes stirring after mixing the parts triethanolamine 0.5 parts by weight The above components with a propeller stirrer to give an ink having a handwriting appearance shine studded greenish blue ground.

Example 2 Ergi Red Gold # 325 (crushed fine pieces of red-gold metal vapor deposition foil, Oike Industry Co., Ltd., particle size 44 μm) 4.0 parts by weight NKW 2107 (pink fluorescent color, Nippon Fluorescent (stock) ) 10.0 parts by weight John Cryl 1535 (resin, styrene-acrylic copolymer, manufactured by Johnson Polymer Co., Ltd.) 10.0 parts by weight NP-15 (dispersant, polyoxyethylene (15) nonylphenyl ether, Nikko Chemicals Co., Ltd. 1.0 parts by weight water 59.4 parts by weight ethylene glycol 7.0 parts by weight glycerin 7.0 parts by weight Proxel GXL (preservative, 1,2-benzisothiazolin-3-one, ICI Japan 0.2 parts by weight TSA739 (antifoaming agent, silicone emulsion, GE Toshiba Silicones Co., Ltd.) 0.2 parts by weight Wa Langham 0.7 parts by weight Triethanolamine 0.5 parts by weight The above components were stirred and mixed with a propeller stirrer for 60 minutes to obtain an ink having a handwriting appearance in which reddish brilliance was scattered on a fluorescent pink background.

Example 3 Luji Silver # 150 (crushed fine pieces of silver-colored metal vapor deposition foil, Oike Industry Co., Ltd., particle size 105 μm) 0.15 parts by weight Luji Violet # 150 (crushed fine fragments of purple metal vapor deposition foil) , Oike Industry Co., Ltd., particle size 105 μm) 0.15 parts by weight LJ Red # 150 (crushed fine pieces of red metal vapor deposition foil, Oike Industry Co., Ltd., particle size 105 μm) 0.15 parts by weight LJ Blue # 150 (crushed fine pieces of blue metal vapor deposition foil, made by Oike Industry Co., Ltd., particle size 105 μm) 0.15 parts by weight ERJ Green # 150 (crushed fine pieces of green metal vapor deposition foil, Oike Industry Co., Ltd.) Manufactured by Oji Industry Co., Ltd., particle size 105 μm) 0.15 parts by weight LZ Red Gold # 150 (crushed fine pieces of red-gold metal vapor deposition foil, manufactured by Oike Industry Co., Ltd., particle size 105 μm) 0.15 Quantitative parts LJG Blue Gold # 150 (crushed fine pieces of blue-gold metal vapor deposition foil, Oike Industry Co., Ltd., particle size 105 μm) 0.15 parts by weight Fuji SP Black 8948 (black colorant, Fuji Pigment Co., Ltd.) ) 5.0 parts by weight John Cryl 450 (resin, styrene-acrylic copolymer, manufactured by Johnson Polymer Co., Ltd.) 10.0 parts by weight NP-18TX (dispersant, polyoxyethylene (18) nonylphenyl ether, Nikko Chemicals 1.0 part by weight water 64.25 parts by weight ethylene glycol 10.0 parts by weight glycerin 7.0 parts by weight Proxel GXL (preservative, 1,2-benzisothiazolin-3-one, ICI Japan (stock) )) 0.2 parts by weight guar gum 1.0 parts by weight triethanolamine 0.5 parts by weight The above components are 60 by a propeller stirrer. After stirring and mixing, violet black areas, a silver-colored, red, was obtained an ink which has a blue, respectively handwriting appearance shine studded greenish.

Example 4 LZY Blue # 325 (crushed micro pieces of blue metal vapor deposition foil, Oike Industry Co., Ltd., particle size 44 μm) 4.0 parts by weight Sandy Super Violet 1103 (purple colorant, Sanyo dye (stock) )) 1.0 parts by weight Jonkryl 1535 (resin, styrene-acrylic copolymer emulsion, manufactured by Johnson Polymer Co., Ltd.) 5.0 parts by weight BO-50 (dispersant, polyoxyethylene (50) oleyl ether) , Nikko Chemicals Co., Ltd. 1.0 parts by weight water 73.2 parts by weight ethylene glycol 7.0 parts by weight glycerin 7.0 parts by weight Proxel GXL (preservative, 1,2-benzisothiazolin-3-one, ICI Japan Co., Ltd.) 0.2 parts by weight xanthan gum 0.9 parts by weight triethanolamine 0.7 parts by weight After stirring and mixing with a propeller stirrer for 60 minutes, an ink having a handwriting appearance in which a blue-based brilliance was scattered on a purple background was obtained.

Example 5 LZY Blue # 325 (crushed micro pieces of blue metal vapor deposition foil, Oike Industry Co., Ltd., particle size 44 μm) 4.0 parts by weight Sandy Super Red 5590 (red colorant, Sanyo dye (stock) )) 2.0 parts by weight John Cryl 775 (resin, styrene-acrylic copolymer, manufactured by Johnson Polymer Co., Ltd.) 7.0 parts by weight NP-10 (dispersant, polyoxyethylene (10) nonylphenyl ether, Nikko Chemicals Co., Ltd. 1.0 parts by weight water 67.2 parts by weight ethylene glycol 10.0 parts by weight glycerin 7.0 parts by weight Proxel GXL (preservative, 1,2-benzisothiazolin-3-one, ICI Japan 0.2 parts by weight TSA739 (antifoaming agent, silicone emulsion, GE Toshiba Silicones Co., Ltd.) 0.2 The amount unit welan gum 0.7 60 minutes stirring after mixing the parts triethanolamine 0.7 parts by weight The above components with a propeller stirrer to give an ink having a handwriting appearance shine studded bluish red ground.

Example 6 LZY Blue Gold # 325 (crushed fine pieces of blue-gold metal vapor deposition foil, Oike Industry Co., Ltd., particle size 44 μm) 4.0 parts by weight Sandy Super Green 1713 (green colorant, Sanyo dye) 2.0 parts by weight Movinyl DM 875 (styrene-acrylic copolymer emulsion, Hoechst Synthetic Co., Ltd.) 5.0 parts by weight NP-15 (dispersant, polyoxyethylene (15) nonylphenyl ether) , Nikko Chemicals Co., Ltd. 1.0 parts by weight water 72.1 parts by weight ethylene glycol 7.0 parts by weight glycerin 7.0 parts by weight Proxel GXL (preservative, 1,2-benzisothiazolin-3-one, ICI Japan Co., Ltd. 0.2 parts by weight TSA739 (antifoaming agent, silicone emulsion, GE Toshiba Silicone ( ) 0.2 parts by weight guar gum 1.0 parts by weight triethanolamine 0.5 parts by weight After stirring and mixing the above components for 60 minutes with a propeller stirrer, it has a handwriting appearance in which a greenish background is studded with a bluish shine. I got ink.

Example 7 LJ Green # 325 (crushed fine pieces of green metal vapor deposition foil, Oike Industry Co., Ltd., particle diameter 44 μm) 4.0 parts by weight Sandy Super Yellow J610 (yellow colorant, Sanyo dye (stock) )) 2.0 parts by weight John Cryl 1535 (resin, styrene-acrylic copolymer, manufactured by Johnson Polymer Co., Ltd.) 10.0 parts by weight NP-18TX (dispersant, polyoxyethylene (18) nonylphenyl ether, Nikko Chemicals Co., Ltd. 1.0 parts by weight water 64.4 parts by weight ethylene glycol 10.0 parts by weight glycerin 7.0 parts by weight Proxel GXL (preservative, 1,2-benzisothiazolin-3-one, ICI Japan 0.2 parts by weight xanthan gum 0.9 parts by weight triethanolamine 0.5 parts by weight The above components 60 min stirring after mixing with a propeller stirrer to give an ink having a handwriting appearance shine studded greenish yellow ground.

Example 8 LRG Red Gold # 325 (crushed fine pieces of red-gold-colored metal vapor deposition foil, Oike Industry Co., Ltd., particle size 44 μm) 2.0 parts by weight NKW 2104 (orange fluorescent color, Nippon Fluorescent (stock) ) 10.0 parts by weight Jonkryl 1535 (resin, styrene-acrylic copolymer, manufactured by Johnson Polymer Co., Ltd.) 10.0 parts by weight BO-50 (dispersant, polyoxyethylene (18) oleyl ether, sunlight Chemicals Co., Ltd. 1.0 parts by weight water 59.1 parts by weight ethylene glycol 7.0 parts by weight glycerin 7.0 parts by weight Proxel GXL (preservative, 1,2-benzisothiazolin-3-one, ICI Japan ( Ltd.) 0.2 parts by weight Welan gum 0.7 parts by weight N-methylmorpholine 1.0 parts by weight The above components are stirred and mixed for 60 minutes with a propeller stirrer. After combination, an ink having a handwriting appearance in which reddish brilliance was scattered on a fluorescent orange background was obtained.

Comparative Example 1 In Example 1, 0.01 part by weight of sodium hydroxide was used instead of 0.5 part by weight of triethanolamine,
Except for increasing the amount of water, the same procedure as in Example 1
An ink having a handwriting appearance in which a greenish glitter was scattered on a blue background was obtained.

Comparative Example 2 The same as Example 2 except that 0.2 part by weight of monoethanolamine was used instead of 0.5 part by weight of triethanolamine and the amount of water was increased. As a result, an ink having a handwriting appearance in which reddish shine was scattered on a fluorescent pink background was obtained.

Comparative Example 3 Example 3 except that 0.5 part by weight of 2-amino-2-methyl-1,3-propanediol was used in place of 0.5 part by weight of triethanolamine. In the same manner as in No. 3, an ink having a handwriting appearance in which violet, silvery, red, blue, and green brilliance was scattered on a black background was obtained.

Comparative Example 4 In the same manner as in Example 4 except that 0.7 parts by weight of triethanolamine was removed and the amount of water was increased, blue-colored brilliance was scattered on the purple background. An ink having a handwriting appearance was obtained.

[0034]

[Table 1]

The following writability test was conducted on the ink compositions according to Examples 1 to 8 and Comparative Examples 1 to 4.

The ink compositions obtained in Examples 1 to 8 and Comparative Examples 1 to 4 were mixed with Hybrid manufactured by Pentel Co., Ltd.
A test sample was prepared by filling the structure of Gel grip DX (product code K230, writing ball diameter: about 1.0 mm), and centrifugal force was applied by a centrifuge to centrifugally defoam bubbles in the ink, and then a test ballpoint pen. Was produced.

This test sample was placed in a thermostatic chamber at 50 ° C. for 30 days, with the pen tip facing downward, with the pen tip closed.
After storing for 60 days and 90 days, after each storage period, a rotation type continuous spiral writing tester (MODEL TS-4
C-20 manufactured by Seiki Kogyo Laboratories), writing speed 7 cm /
100 under the condition of second, writing angle 70 °, writing load 100g
m Write down. The writing paper is fine paper (JIS P320
1 Writing paper A) was used. After writing, observe the handwriting, and if discontinuities or thin parts appear in places on the writing line, measure the length and show the results in the "Writability" column of Table 1. It was The results in the table are the total length.

As described above in detail, when the ink composition of the present invention is used in combination with a ballpoint pen using a writing ball having a specific surface state, it is possible to obtain an ink having high stability over time. It is an excellent one to get handwriting without line skipping.

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] July 31, 2001 (2001.7.3)
1)

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0017

[Correction method] Change

[Correction content]

Water can be used as the main solvent of the liquid medium for making the ink. Further, conventionally known for various qualities as an ink, for example, for the purpose of preventing ink from freezing at low temperature, preventing ink from drying with a pen tip, dispersing medium of pigment, dissolving agent of dye, dissolving / dispersing of viscosity adjusting agent, etc. It is possible to use the water-soluble organic solvent. Specific examples of the water-soluble organic solvent include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, polyethylene glycol, hexylene glycol, 1,3-butylene glycol, thiodiethylene glycol, 1,5-
Glycols such as pentanediol and glycerin, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol monoethyl ether, dipropylene glycol Glycol ethers such as monoethyl ether and N-medium
Cyl-2-pyrrolidone and the like can be mentioned . These water-soluble organic solvents can be used alone or in combination.
The amount used is preferably 10 to 60% by weight based on the total amount of the ink composition.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Toshiyuki Wakae             4-1-8 Yoshimachi, Soka-shi, Saitama Pentel stock             Ceremony company grass processing plant F-term (reference) 2C350 GA03 HA09 HA12 NA19                 4J037 AA04 CC00 DD05 EE03 EE28                       EE29 FF05 FF06 FF07 FF08                 4J039 AB01 AD03 AD08 AD09 AD15                       BA01 BC35 BD02 BE01 BE12                       CA06 GA27

Claims (6)

[Claims] 1. An ink composition comprising at least a part or whole of metal fine particles coated with a transparent colorless or colored resin, a liquid medium, and a tertiary amine. 2. The ink composition according to claim 1, wherein the pigment is a metal foil powder obtained by crushing a metal foil having a resin layer formed on the surface thereof. 3. The ink composition according to claim 1, wherein the tertiary amine is triethanolamine. 4. The pigment is 1 in the total amount of the ink composition.
The ink composition according to any one of claims 1 to 3, wherein the ink composition is contained in an amount of 8 wt%. 5. The ink composition according to claim 1, which contains a natural polysaccharide or a derivative thereof. 6. A writing member which is a sintered body of silicon carbide and has pores formed on the surface with a depth of 0.3 μm or more and 1.0 μm or less, and an average pore diameter of 1 μm or more and 10 μm or less,
Average number of holes on the ball is 1 / 50μcm ² or more 3
A ball-point pen tip comprising a ball having a number of particles / 50 μcm ² or less and a ball holder that projects and holds the ball at the tip thereof, at the tip of the ink cylinder containing the ink according to any one of claims 1 to 5. , A ballpoint pen that is connected directly or through a joint member.