JP2003012973A - Ink and ball point pen using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a sheen ink composition which is filled in a ball point pen and used and creates in the writing a sheen feeling different from the color of the writing. SOLUTION: The ink comprises 2 wt.% to 8 wt.%, based on the total ink weight, crushed fine fragments of a metal deposited foil having been colored to a chromatic color which have a particle diameter of 20 μm to 100 μm.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ink using a reflective coloring agent such as a pearl pigment, glass flakes or a metal powder pigment, and a writing member 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 including a ball as a base and a ball holder that holds the ball by projecting the tip.

[0002]

2. Description of the Related Art Heretofore, inks for forming handwriting using a reflective coloring material having a glittering property such as pearl pigments, glass flakes and metal powder pigments have been known. It is mainly for obtaining a metallic luster of its own color such as silver, or for obtaining a gold or metallic color by mixing with a chromatic colorant.

For example, an ink using a pearl pigment is
JP-A-5-117569 and JP-A-9-2682.
No. 70, etc., and an ink using glass flakes is disclosed in Japanese Patent Laid-Open No. 2000-72995, and an example of an ink using a metal powder pigment is WO98 / 404.
Japanese Patent Publication No. 53-27975 discloses an example in which metal powder of crushed fine particles of a metal vapor deposition foil is used in Japanese Patent Publication No. 41-41.

[0004]

[Problems to be Solved by the Invention] An ink that produces an entertaining handwriting in which another color different from the handwriting color is glittering in the handwriting by using a colored material having a glittering property different from the handwriting color Is not suggested.

Further, the above-mentioned glittering color material is
Since it is necessary to reflect light, if a flat plate-like or flaky pigment having a reflecting surface is used, it is possible that the ink is allowed to flow through a minute gap between members such as a ballpoint pen. Due to the shape, the above pigment is hard to flow on the ink and flow, and residual clogging may occur inside the ballpoint pen tip.

An object of the present invention is to provide a glitter ink composition in which the color of the handwriting produces the tone of the handwriting and the luster of a different color tone among the colors of the handwriting. To obtain a ballpoint pen that can be obtained continuously.

[0007]

That is, according to the present invention, a reflective colorant having a particle diameter of 20 μm or more and 100 μm or less colored in a chromatic color is used in an amount of 2% by weight or more and 8% by weight or less with respect to the total amount of the ink. The gist is an ink containing a colorant having a color different from the colored color.

The present invention will be described in detail below. The reflective pigment used in the ink of the present invention is used for the purpose of producing a bright feeling different from the color of handwriting. The crushed fine pieces of the metal vapor deposition foil are commercially available as metallic powders. For example, Elgi Silver # 325 and Red can be used.
Gold # 325 and Blue Gold # 32
5, Red # 325, Blue # 325, Green # 325, Violet # 32
5, Same Black # 325, Same Copper #
325 (particle size is 44 μm or more), ergi Silver
# 500, Gold # 500 (above grain size 2
8 μm) (all manufactured by Oike Industry Co., Ltd.). These crushed fine pieces of metal vapor deposition foil can be used alone or in combination of two or more kinds.

The reflective pigment used in the present invention can be used in an amount of 2.0 to 8.0% by weight. If it is 2% or less, the glitter may be inferior depending on the brightness, and if it is 8% or more, the color tone of the metal vapor deposition foil may be emphasized, resulting in a single color.

The size of the reflective pigment used is preferably 100 μm or less, more preferably 60 μm or less in average particle diameter. This is because if the particle size is larger than 100 μm, the ink may be clogged at the pen tip and writing may not be possible.

Examples of a pen tip for ejecting such a reflective pigment to form a handwriting include a marker using a fiber bundle, a valve-type applicator, and the like. A ball-point pen having a ball-point pen tip that projects and holds is preferably used. In particular, the ball, which is a writing member that transfers the 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 of 1 μm. It is preferably 10 μm or less. By using such a ball, even if the reflective pigment having the above-mentioned particle size is used, the ink can be easily applied to the ball and is ejected well, so that it is possible to continuously form good handwriting. Is something that can be done.

The colorant used in the present invention is used for providing contrast with the original color tone of the colored reflective pigment. That is, when a green colorant is used, if a gold reflective pigment is used, the reflective pigment on the green handwriting shines golden like a star in the night sky, or if a blue reflective pigment is used. , You can get a green handwriting with some glittering blue. When using a pigment as a colorant, a conventionally known pigment can be used, for example,
C. I. Pigment Yellow 1 and 14,
Id 17, Id 42, Id 81, Id 83, C.I. I. P
igment Orange 13, ibid. 34, C.I. I.
Pigment Red 5, the same 17, the same 22,
Ibid. 101, ibid. 122, C.I. I. Pigment G
reen 7, ibid 36, C.I. I. Pigment B
lue 15, the same 15-1, the same 15-3, the same 2
9, C.I. I. Pigment Violet 19, 23, C.I. I. Pigment Black 7, the same
11 etc. are mentioned.

In the case of a pigment, a commercially available water-dispersible type is preferably used because the handling property and the productivity are enhanced. As a specific example of the water dispersion type, Ryudye-W
Series (manufactured by Dainippon Ink and Chemicals, Inc.), Sand
ye Super series (Sanyo Pigment Co., Ltd.), E
M Color series, LIOFAST Colo
r series (manufactured by Toyo Ink Mfg. Co., Ltd.) and the like.

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
Yellow 23, 42, C.I. I. Acid
Orange 19, 56, C.I. I. Acid R
ed 18, ibid. 51, 87, C.I. I. Acid Vi
olet 49, C.I. I. Acid Blue 1, ibid 7, ibid 15, ibid 90, C.I. I. Acid Gre
en 3, ibid 9, C.I. I. Acid Brown 1
3, C.I. I. Acid Black 1, the same 2, the same
3, the same 187, the same 194, the same 24, the same 52, the same 50, the same 31, the same 52: 1, the same 192: 2, the same 131, the same 172, the same 63s, the same 7, and the same 6
0, 107, 58, 60, 132, 140, 112, 155, 109, 109
26, 207, 170, 132, 22
2, 194, 63, 164, and basic dyes include C.I. I. Basic Yellow 11,
C. I. Basic Orange 21, C.I. I. B
asic Red 1, 13 and C.I. I. Basic
Violet 3C. I. Basic Blue
1, the same 7, C.I. I. Basic Green 1, C.I.
I. Basic Black 2 and 8, direct dyes include C.I. I. Direct Yellow 1, the same,
23, C.I. I. Direct Orange 8, C.I.
I. DirectRed 2, 13 and C.I. I. Di
rect Violet 1, C.I. I. Direct
Blue 1, 86, C.I. I. Direct Green
n6, C.I. I. Direct Brown 95,
C. I. Direct Black22, ibid 32, ibid 38, ibid 17, ibid 19, ibid 162: 1, ibid 5
1, the same 154, the same 169, the same 154, the same 117,
173 and the like. The amount of the colorant used in the present invention is preferably equal to or less than that of the metal foil powder.

It is preferable to use a thickener in order to prevent sedimentation of the reflective pigment and to obtain appropriate viscosity physical properties as an ink for ballpoint pens. For example, seed polysaccharide guar gum, locust bean gum and its derivatives, microbial xanthan gum, welan gum and Alcali.
genes latus B-16 strain B-16 polymer (alka gum), which is an acid polysaccharide produced in detail, seaweed polysaccharide carrageenan, alginic acid and its derivatives, resin polysaccharide tarragant gum, cellulosic sodium carboxymethyl cellulose, hydroxypropyl Cellulose or the like can be used. In particular, polysaccharides have relatively stable physical properties even after being stored for a long period of time, and also have a great decrease in viscosity due to rotation of the ball during writing, and thus have excellent writing characteristics as a ballpoint pen.

As the liquid medium for forming the ink, water can be used, as well as organic solvents known to be used in various inks.

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

In addition to the above components, various conventional additives used in inks can be used. For example,
A water-soluble organic solvent can be used for the purpose of preventing ink from drying with a pen tip and preventing freezing of ink 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, and ethylene glycol. 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, a resin soluble or dispersible in a liquid medium used as a fixing agent can be used for fixing solid matters in the ink such as a reflective pigment and a coloring agent to a writing surface such as paper. it can. Specifically, styrene-
Alkali metal salt of acrylic acid copolymer, amine salt, ammonium salt, alkali metal salt of α-methylstyrene-acrylic acid copolymer, amine salt, ammonium salt, alkali of styrene-acrylic acid ester-acrylic acid copolymer Examples thereof include water-soluble resins such as metal salts, amine salts, and ammonium salts, acrylic resins, vinyl acetate resins, water-insoluble resins such as styrene-butadiene copolymers. 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, preservatives such as benzothiazoline and omadine, rust preventives such as benzotriazole, anionic and nonionic surfactants, and defoaming agents. Various additives such as can be used.

[0020]

[Examples] Example 1 LJ Green # 325 (crushed fine pieces of green metallized foil, manufactured by Oike Industry Co., Ltd., particle size: 44 μm) 4.0 parts by weight Sandy Super Blue 1808 (blue colorant, Sanyo) Dyestuff Co., Ltd.) 2.0 parts by weight John Cryl 1535 (resin, styrene-acrylic acid copolymer, manufactured by Johnson Polymer Co., Ltd.) 10.0 parts by weight Water 65.7 parts by weight Ethylene glycol 10.0 parts by weight Glycerin 7.0 parts by weight Proxel GXL (preservative, 1,2-benzisothiazolin-3-one, manufactured by ICI Japan Co., Ltd.) 0.2 parts by weight TSA739 (antifoaming agent, silicone emulsion, GE Toshiba Silicone Co., Ltd.) 0.2 parts by weight xanthan gum 0.9 parts by weight The above ingredients are stirred and mixed for 60 minutes with a propeller stirrer to give a blue-green glow. To obtain a key.

Example 2 Eruji Green # 325 (crushed fine pieces of green metallized foil, Oike Industry Co., Ltd., particle size 44 μm) 4.00 parts by weight Sandy Super Blue 1808 (blue colorant, Sanyo dye) Co., Ltd.) 2.00 parts by weight John Cryl 1535 (resin, styrene-acrylic acid copolymer, manufactured by Johnson Polymer Co., Ltd.) 10.00 parts by weight water 66.45 parts by weight ethylene glycol 10.00 parts by weight glycerin 7.00 parts by weight Proxel GXL (preservative, 1,2-benzisothiazolin-3-one, manufactured by ICI Japan Co., Ltd.) 0.20 parts by weight TSA739 (antifoaming agent, silicone emulsion, GE Toshiba Silicone Co., Ltd.) 0.20 parts by weight Alka gum 0.15 parts by weight The above components are stirred and mixed with a propeller stirrer for 60 minutes to obtain blue. To give the ink of the above green glow.

Example 3 LRG Red Gold # 325 (crushed fine pieces of red-gold-colored metal vapor deposition foil, Oike Industry Co., Ltd., particle size 44 μm) 8.0 parts by weight NKW 2107 (pink fluorescent color, Japanese fluorescent ( Co., Ltd.) 14. 0 parts by weight John Cryl 1535 (resin, styrene-acrylic acid copolymer, manufactured by Johnson Poly, Mar. Ltd.) 10.0 parts by weight water 52.9 parts by weight ethylene glycol 7.0 parts by weight glycerin 7.0 parts by weight Proxel GXL (preservative, 1,2-benzisothiazolin-3-one, manufactured by ICI Japan Co., Ltd.) 0.2 parts by weight TSA739 (antifoaming agent, silicone-based emulsion, manufactured by GE Toshiba Silicone Co., Ltd.) 0.2 Parts by weight Welan gum 0.7 parts by weight The above components were stirred and mixed with a propeller stirrer for 60 minutes to obtain an ink of pink color and red gold color shine.

Example 4 LRG Red Gold # 325 (crushed fine pieces of red-gold-colored metal vapor deposition foil, Oike Industry Co., Ltd., particle size 44 μm) 8.0 parts by weight NKW 2107 (pink fluorescent color, Japanese fluorescent ( Co., Ltd.) 14. 0 parts by weight John Cryl 1535 (resin, styrene-acrylic acid copolymer, manufactured by Johnson Poly Co., Ltd.) 10.0 parts by weight water 53.4 parts by weight ethylene glycol 7.0 parts by weight glycerin 7.0 parts by weight Proxel GXL (preservative, 1,2-benzisothiazolin-3-one, manufactured by ICI Japan Co., Ltd.) 0.2 parts by weight TSA739 (antifoaming agent, silicone-based emulsion, manufactured by GE Toshiba Silicone Co., Ltd.) 0.2 Parts by weight Alka gum 0.2 parts by weight The above components were stirred and mixed with a propeller stirrer for 60 minutes to obtain an ink having a pink color and a red gold color shine.

Example 5 Luji Silver # 500 (crushed fine pieces of silver-colored metal vapor deposition foil, Oike Industry Co., Ltd., particle size 44 μm) 2.00 parts by weight Luji Violet # 325 (crushed fine powder of purple metal vapor deposition foil) Piece, Oike Industry Co., Ltd., particle size 44 μm) 2.00 parts by weight Fuji SP Black 8948 (black colorant, Fuji Dye Co., Ltd.) 2.00 parts by weight Jonkuril 450 (resin, styrene-acrylic acid) Copolymer, manufactured by Johnson Polymer Co., Ltd. 10.00 parts by weight Water 66.65 parts by weight Ethylene glycol 10.00 parts by weight Glycerin 7.00 parts by weight Proxel GXL (preservative, 1,2-benzisothiazoline-3- ON, manufactured by ICI Japan Co., Ltd.) 0.20 parts by weight Alka gum 0.15 parts by weight The above components are stirred and mixed with a propeller stirrer for 60 minutes. Then, a black upper purple brilliant ink was obtained.

Example 6 LZY Blue # 325 (crushed minute pieces of blue metal vapor deposition foil, Oike Industry Co., Ltd., particle size 44 μm) 2.00 parts by weight Sandy Super Violet 1103 (purple colorant, Sanyo dye (stock) )) 0.70 parts by weight John Cryl 1535 (fixing agent, emulsion of styrene-acrylic acid copolymer, manufactured by Johnson Polymer Co., Ltd.) 5.00 parts by weight water 77.97 parts by weight ethylene glycol 7.00 parts by weight Glycerin 7.00 parts by weight Proxel GXL (preservative, 1,2-benzisothiazolin-3-one, manufactured by ICI Japan Co., Ltd.) 0.20 parts by weight Alkagum 0.13 parts by weight The above components are mixed with a propeller stirrer for 60 minutes. The mixture was stirred and mixed to obtain an ink having a purple color and a blue color.

Example 7 LZY Blue Gold # 325 (crushed fine pieces of blue-gold metal vapor deposition foil, Oike Industry Co., Ltd., particle size 44 μm) 4.00 parts by weight Sandy Super Blue 1808 (blue colorant, Sanyo dye) KK) 2.00 parts by weight John Cryl 1535 (fixing agent, emulsion of styrene-acrylic acid copolymer, manufactured by Johnson Polymer Co., Ltd.) 5.00 parts by weight water 74.65 parts by weight ethylene glycol 7.00 Parts by weight glycerin 7.00 parts by weight Proxel GXL (preservative, 1,2-benzisothiazolin-3-one, manufactured by ICI Japan Co., Ltd.) 0.20 parts by weight alka gum 0.15 parts by weight With the propeller stirrer The mixture was stirred and mixed for 60 minutes to obtain an ink having a blue-blue-blue brilliance.

Example 8 LZY Blue # 325 (crushed micro pieces of blue metal vapor deposition foil, Oike Industry Co., Ltd., particle size 44 μm) 6.00 parts by weight Sandy Super Red 5590 (red colorant, Sanyo dye (stock) )) 2.00 parts by weight John Cryl 775 (fixing agent, emulsion of styrene-acrylic acid copolymer, manufactured by Johnson Polymer Co., Ltd.) 10.00 parts by weight water 67.62 parts by weight ethylene glycol 7.00 parts by weight Glycerin 7.00 parts by weight Proxel GXL (preservative, 1,2-benzisothiazolin-3-one, manufactured by ICI Japan Co., Ltd.) 0.20 parts by weight Alkagum 0.18 parts The above components are stirred with a propeller stirrer for 60 minutes. The mixture was mixed to obtain an ink having a red color and a blue color.

Example 9 LRG Red Gold # 325 (crushed fine pieces of red-gold-colored metal vapor deposition foil, Oike Industry Co., Ltd., particle size 44 μm) 4.0 parts by weight NKW 2104 (orange fluorescent color, Japanese fluorescent ( Co., Ltd.) 10.0 parts by weight John Cryl 1535 (resin, styrene-acrylic acid copolymer, Johnson Poly, Mar Co., Ltd.) 10.0 parts by weight water 61.4 parts by weight ethylene glycol 7.0 parts by weight Part Glycerin 7.0 parts by weight Proxel GXL (preservative, 1,2-benzisothiazolin-3-one, manufactured by ICI Japan Co., Ltd.) 0.2 parts by weight TSA739 (antifoaming agent, silicone emulsion, GE Toshiba Silicone ( Co., Ltd.) 0.2 parts by weight Alka gum 0.2 parts by weight The above components are stirred and mixed with a propeller stirrer for 60 minutes to obtain an orange-red-gold-glow ink. .

Example 10 LJ Green # 325 (crushed fine pieces of green metal vapor deposition foil, Oike Industry Co., Ltd., particle size 44 μm) 5.00 parts by weight Sandy Super Yellow J610 (yellow colorant, Sanyo dye ( Co., Ltd.) 1.00 parts by weight Johncryl 450 (resin, styrene-acrylic acid copolymer, manufactured by Johnson Polymer Co., Ltd.) 10.00 parts by weight water 66.64 parts by weight ethylene glycol 10.00 parts by weight glycerin 7 0.000 parts by weight Proxel GXL (preservative, 1,2-benzisothiazolin-3-one, manufactured by ICI Japan Co., Ltd.) 0.20 parts by weight alka gum 0.16 parts by weight The above components are stirred and mixed for 60 minutes with a propeller stirrer. As a result, an ink having a yellow and green glow was obtained.

Example 11 A purple ink was obtained in the same manner as in Example 6 except that the amount of LJG Blue # 325 of Example 6 was changed to 1.0% by weight and the amount of water was increased accordingly.

Comparative Example 1 Sandy Super Blue 18 of Example 1
Ink was obtained in the same manner as in Example 1 except that 08 (blue colorant) was added and the amount of water was increased.

Comparative Example 2 An ink having a red-gold color shine was obtained in the same manner as in Example 4 except that NKW 2107 (pink fluorescent color) of Example 4 was removed and the amount of water was increased accordingly.

Comparative Example 3 An ink having a green brilliance was obtained in the same manner as in Example 1 except that the amount of LJ Green # 325 of Example 1 was increased to 9.0% by weight and the amount of water was reduced accordingly.

[0034]

The inks obtained in Examples 1 to 11 and Comparative Examples 1 to 3 are used in the Hybrid Ge manufactured by Pentel Co., Ltd.
l grip DX (product code K230, writing ball diameter of about 1.0 mm) was filled as a test sample, and the letters "Naga" were written on high-quality paper (JIS P3201 writing paper A), and the color of the handwriting Was visually confirmed.
The results are shown in Table 1.

For each ink, the above-mentioned Hybri
In the structure of d Gel grip DX, the writing ball is silicon carbide, and the surface state is 0.3 μm in depth.
As described above, the average pore size (= 0.1 μm from the surface) (=
The writing test is performed by the test method described in JIS S6054 by using 24 holes having a circumscribed circle diameter- (circumscribed circle diameter-inscribed circle diameter) / 2) of 1 μm or more in a 50 μm square. went. The weight of the ball-point pen used in the test was measured every 50 m writing, and the reduced amount was estimated as the amount of ink that became the handwriting, and the ink discharge amount until the ink was not discharged was examined. The results are shown in Table 2.

[0036]

[Table 1]

[0037]

[Table 2]

As described above in detail, the ink according to the present invention is capable of producing an entertaining handwriting in which another color different from the color of the handwriting glitters in the handwriting. Further, when used in combination with a ballpoint pen that uses a writing ball having a specific surface state, it is excellent in that good ink ejection is maintained and handwriting without blurring is obtained.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Toshiyuki Wakae             4-1-8 Yoshimachi, Soka-shi, Saitama Pentel stock             Ceremony company grass processing plant (72) Inventor Yuichi Takahashi             4-1-8 Yoshimachi, Soka-shi, Saitama Pentel stock             Ceremony company grass processing plant F-term (reference) 2C350 HA09 HA10 KC01                 4J039 AB01 BA06 BE01 BE03 BE04                       BE05 BE23 CA06 EA33 GA27

Claims (6)

[Claims] 1. A chromatically colored reflective colorant having a particle size of 20 μm or more and 100 μm or less based on the total amount of the ink.
An ink containing from 8% by weight to 8% by weight and a colorant having a color different from the color of the reflective colorant. 2. The ink according to claim 1, wherein the reflective colorant is crushed metal foil powder coated with a transparent colored resin layer. 3. The ink according to claim 1, wherein the reflective colorant is a crushed fine piece of a metal vapor deposition foil coated with a transparent colored resin layer. 4. The ink according to claim 1, which contains a natural polysaccharide or a derivative thereof as a thickener. 5. The ink according to any one of claims 1 to 4, wherein the liquid medium contains at least water. 6. A ball as a writing member, which is a sintered body of silicon carbide and has a hole 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, and this ball. A ball-point pen tip composed of a ball holder that holds the ink by projecting from the tip is connected to the tip of the ink cylinder containing the ink according to any one of claims 1 to 5 directly or via a joint member. Ballpoint pen.