JPH07118592A - Water-base ballpoint ink with metallic luster - Google Patents

Abstract

PURPOSE:To obtain the title ink which gives a well-defined writing with metallic luster and has good long-term stability without deterioration even in long-term storage. CONSTITUTION:The ink has a viscosity (measured with a type E viscometer at an ST rotor speed of 1rpm, at 25 deg.C) of 10,000 to 150,000 and contains at least a pearlescent pigment perferably in an amount of 5-20wt.%, a water-soluble thickening resin comprising, e.g. a seed polysaccharide, such as guar gum or locust bean gum, its derivative or a microbial xanthan gum, a water-soluble organic solvent, such as glycol or glycerin, preferably in an amount of 5-40wt.% and water.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a water-based metallic luster color ink for ballpoint pens that can be used to obtain handwriting in metallic luster colors such as gold and silver using a pearl pigment, and to obtain handwriting in metallic luster color even after long-term storage. The present invention relates to a water-based metallic luster color ink for ball-point pens that is capable of producing a good ink discharge property.

[0002]

2. Description of the Related Art Conventionally, various inks using aluminum powder, bronze powder, and pearl pigment as pigments have been proposed in order to obtain a handwriting of metallic luster colors such as gold and silver. For example, Japanese Examined Patent Publication No. 62-37678 discloses a metal powder pigment such as aluminum powder, an oil-soluble dye, a resin, and a solvent, and the dye permeates and diffuses around the handwriting formed by the metal powder pigment to form a contour. Dual color ink compositions that produce a line effect are disclosed. Japanese Patent Publication No. 56109/1989 discloses a fine metal powder such as a surface-treated aluminum powder, a resin and a solvent, which has a smooth ink outflow from various marking pens and is easy to disperse in practical use. A metallic gloss ink for a marking pen having the same is disclosed. Further, JP-A-60-186573 discloses that a solvent and a thickening resin soluble in the solvent, a metal powder pigment and a coloring pigment are each contained in at least a required amount, and a high viscosity not less than a required value. Disclosed is an ink having a water-free oily metallic tone characterized in that it is suitable for use in a pressure ballpoint pen.

Further, in JP-A-1-210478, for the purpose of preventing coating stains due to pinholes, an acetylene alcohol derivative is added as an additive to the ink main component consisting of resin, aluminum paste and water. Added aqueous metallic inks are disclosed.
Further, JP-A-5-117569 discloses an aqueous ink using a pearl pigment which is stable against water, instead of the metal powder pigment.

[0004]

However, there is no proposal of a water-based metallic luster color ink which can be used for a ballpoint pen. It is necessary that the ink for a ballpoint pen can be used without redispersing the pigment. Nevertheless, none of the previously proposed inks are aqueous and do not cause the pigment to settle. For example, Japanese Patent Publication 62-
The inks described in Japanese Patent No. 37678 and Japanese Patent Publication No. 1-56109 are oil-based and are conscious of marking pens. The marking pen is one in which a stirring member such as a metal ball is stored in the ink storage chamber, and the writing instrument is shaken at the time of use to re-disperse the precipitated aluminum powder. That is, in the ink compositions according to these inventions, the aluminum powder precipitates in a short time. The ink disclosed in JP-A-60-186573 has little pigment sedimentation,
It is oily. Further, although the inventions described in Japanese Patent Publication Nos. 1-210478 and 5-117569 are water-based inks, they are conscious of marking pens as described above.

An object of the present invention is to provide a water-based metallic luster color ink for ballpoint pens which can be used well even after storage for a long period of time.

[0006]

The present invention contains at least a pearl pigment, a thickening resin, a solvent and water, and has a viscosity of 1 or less.
A water-based metallic luster color ink for a ball-point pen having a 0000 to 150000 cps (ST rotor of E type viscometer, 1 rpm, 25 ° C.) is a gist.

The details will be described below. The pearl pigment used in the present invention is used as a metallic luster colorant. The pearl pigment is obtained by coating the surface of natural mica with a metal oxide having a high refractive index such as titanium oxide or iron oxide. The average particle size of the pearl pigment is preferably 5 to 60 μm. If the average particle size is 5 μm or less, the pearl luster decreases, and the metallic luster of the handwriting easily decreases.
When it is at least μm, ink ejection tends to be lowered when applied to a ball-point pen tip that has been generally used conventionally.

Commercially available pearl pigments include Ir
iodin 100 (average particle size: 10 to 60 μm, the same below), 103 (10 to 50) or more, silver color, Iriod
in300 (10-60), the same 302 (5-20), the same 323 (5-20) or more, gold color, Iriodin 504
(10-60), 524 (5-20) or more, red, I
riodin 502 (10-60 μm), 520 (5
.About.20 .mu.m) or more, and copper color (manufactured by Merck Japan Co., Ltd.) and the like. They are acid and alkali resistant, insoluble in water but readily dispersible in aqueous systems. Pearl pigment is 5 to 2 for water-based metallic luster color ink for ballpoint pens.
0% by weight is preferably used.

The thickening resin is used as a water-based ink composition for ballpoint pens, to prevent sedimentation of pearl pigments, for example, to prevent ink leakage from the pen tip, to properly discharge ink.
It is used for the purpose of preventing dirt on the pen tip and bloating.
For ball-point pens used in a normal atmosphere in which one end of the ink containing tube is open, seed gum guar gum, locust bean gum and its derivatives, and microbial xanthan gum can be preferably used. In addition, for pressure type ballpoint pens suitable for high speed writing and upward writing with a pen tip, the amount of the resin added is increased, in addition, carrageenan of seaweed polysaccharide, alginic acid and its derivatives, resin polysaccharide tarragant gum, cellulose derivative, A synthetic polymer such as polyethylene oxide or sodium polyacrylate can be used. The amount of the thickening resin used varies greatly depending on the type of the resin used, and is therefore set so as to exhibit an appropriate viscosity. Its viscosity is 10,000-1500
00cps (ST rotor of E type viscometer, 1 rpm, 25
℃). When used for a ballpoint pen, the decrease in ink viscosity due to the shearing force of the ball rotation affects the amount of ink discharged from the pen tip. The ratio of the viscosity when measured and the value measured at 10 rpm is preferably 3.0 or more.

The water-soluble organic solvent is used for various qualities as a water-based ink for ballpoint pens, for example, for the purpose of preventing ink drying at the pen tip and preventing ink freezing at low temperatures. Specifically, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, polyethylene glycol, 1,3-butylene glycol, thiodiethylene glycol, glycols such as glycerin, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether,
2-Pyrrolidone, triethanolamine and the like can be used alone or in combination. The amount used is preferably 5 to 40% by weight with respect to the total amount of the water-based metallic luster color ink for ballpoint pens.

Water is used as the main solvent.

In addition to the above components, wetting agents such as urea, ethyleneurea and thiourea, lubricants, preservatives such as benzothiazoline and omadine, anticorrosives such as benzotriazole, anion and nonionic. Various additives such as the above-mentioned surfactants, and dyes such as acid dyes, basic dyes and direct dyes, and colored pigments can be used when producing hues of various metallic luster colors.

In producing the metallic luster color ink for ballpoint pens of the present invention, various conventionally known methods can be adopted. For example, it can be easily obtained by blending the above-mentioned components and stirring and mixing with a stirrer such as a Henschel mixer, or mixing and grinding with a disperser such as a ball mill.

[0014]

The effect of the aqueous metallic luster color ink for ballpoint pens of the present invention on the stability over time by suppressing sedimentation of the pearl pigment even during long-term storage is presumed as follows. Since the usual ink composition for a ballpoint pen of the present invention has such a high viscosity that the fluidity of the ink is not impaired, the pearl pigment is fixed between the resins, and as a result, the pearl pigment can be prevented from settling. Further, since the pearl pigment does not cause gelation, hydrolysis or partial insolubilization with respect to the resin, the viscosity of the ink does not increase or decrease.

[0015]

【Example】

Example 1 Iriodin 302 (manufactured by Merck Japan Ltd.) 10.0 parts by weight Jaguar CMHP (gargar derivative, manufactured by Sansho Co., Ltd.) 1.0 part by weight ethylene glycol 15.0 parts by weight glycerin 10.0 parts by weight water 62 9 parts by weight Proxel XL-2 (preservative, manufactured by ICI Japan Co., Ltd.) 0.1 parts by weight NP-10 (dispersant, manufactured by Nikko Chemicals Co., Ltd.) 1.0 parts by weight Other than Jaguar CMHP After being placed in a ball mill for 10 hours for dispersion treatment, Jaguar CMHP was added and the treatment was performed again for 1 hour to obtain a golden ink having a viscosity of 25,000 cps (E type viscometer, 1 rpm, 25 ° C.). This golden ink is a ballpoint pen (made of a transparent ink containing tube consisting of a polypropylene hollow shaft cylinder with a nickel-white ballpoint pen tip (ball material: cemented carbide) connected at one end)
When filled in and writing on the paper surface, clear golden handwriting without bleeding was obtained. Also, 1/10 rpm of this ink
The viscosity ratio was 3.6.

Example 2 Iriodin 103 (manufactured by Merck Japan Ltd.) 10.0 parts by weight Locust bean gum 2.0 parts by weight Propylene glycol 20.0 parts by weight Ethylene glycol 10.0 parts by weight Water 56.9 parts by weight Proxel GXL (Preservative, manufactured by ICI Japan Co., Ltd.) 0.1 part by weight BT-12 (dispersant, manufactured by Nikko Chemicals Co., Ltd.) 1.0 part by weight The above components are dispersed in a ball mill for 12 hours to obtain a viscosity. 35000 cps (E type viscometer, 1 rpm, 25 ° C)
To obtain a silver ink. A ballpoint pen was filled with this silver ink in the same manner as in Example 1, and writing was performed on the paper surface. As a result, clear silver-colored handwriting without bleeding was obtained. In addition, 1 of this ink
The viscosity ratio at / 10 rpm was 3.1.

Example 3 Iriodin 524 (manufactured by Merck Japan Ltd.) 10.0 parts by weight Zansan gum 1.0 part by weight Ethylene glycol 10.0 parts by weight Glycerin 10.0 parts by weight Water 67.9 parts by weight Proxel XL-20 1 part by weight NP-10 1.0 part by weight The above components were dispersed in a ball mill for 2 hours to obtain a viscosity of 3
A metallic gloss red ink of 0000 cps (E type viscometer, 1 rpm, 25 ° C.) was obtained. When this red ink was filled in a ball-point pen in the same manner as in Example 1 and writing was performed on the paper surface, a red handwriting with a clear metallic gloss color without bleeding was obtained. The viscosity ratio of this ink at 1/10 rpm is 6.
It was 0.

Example 4 Iriodin 302 10.0 parts by weight Hydroxyethyl cellulose 5.0 parts by weight Ethylene glycol 17.0 parts by weight Glycerin 8.0 parts by weight Water 61.9 parts by weight Proxel GXL 0.1 parts by weight NP-10 1. 0 parts by weight The above components are dispersed in a ball mill for 3 hours to obtain a viscosity of 1
A golden ink of 10,000 cps (E type viscometer, 1 rpm, 25 ° C.) was obtained. This gold-colored ink is an ink containing tube made of a stainless steel barrel having a pressure ballpoint pen (stainless ballpoint pen tip (ball material: cemented carbide) connected at one end, and a pressure of 3.0 kg / cm in the containing tube.
^It was filled up with the product which was sealed with a tail plug by multiplying by ² ) and then written on the surface of the paper. As a result, a clear golden handwriting without bleeding was obtained.

Comparative Example 1 Jaguar CMHP of Example 1 was reduced to 0.6 parts by weight,
A viscosity of 7000 cps (E type viscometer, 1 rpm, 2 rpm) was obtained in the same manner as in Example 1 except that water was added by the reduced amount.
A golden ink of 5 ° C.) was obtained. This golden ink was used in Example 1.
When filling in a ballpoint pen and writing on the paper like the above,
I got a clear golden handwriting without bleeding. The viscosity ratio of this ink at 1/10 rpm was 2.5.

Comparative Example 2 The Jaguar CMHP of Example 1 was increased to 2.8 parts by weight,
A viscosity of 180,000 cps (E-type viscometer, 1 rp) was obtained in the same manner as in Example 1 except that water was reduced by the increased amount.
m, 25 ° C.) was obtained. When this ball-point pen was filled with this golden ink in the same manner as in Example 1 and writing was performed on the paper surface, no writing was possible. Also, 1/10 of this ink
The rpm viscosity ratio was 5.0.

Comparative Example 3 The procedure of Example 2 was repeated except that aluminum powder (WB0230, manufactured by Toyo Aluminum Co., Ltd.) was used instead of Iriodin 103 of Example 2, and the viscosity was 36000c.
A silver ink of ps (E type viscometer, 1 rpm, 25 ° C.) was obtained. When this silver-colored ink was filled in a ball-point pen in the same manner as in Example 1 and writing was performed on the paper surface, a clear silver-colored handwriting without bleeding was given. Also, 1/10 rpm of this ink
The viscosity ratio was 3.2.

With respect to the water-based metallic luster color inks for ballpoint pens obtained in Examples 1 to 4 and Comparative Examples 1 to 3, a viscosity change test,
A writing test and a sedimentation test were performed. The results are shown in Table 1.

[0023]

[Table 1]

(Notes in Table 1) Comparative Example 1; Viscosity change test cannot be performed due to sedimentation of pearl pigment. The writing test cannot be measured because the pearl pigment settles during centrifugal defoaming. The sedimentation test cannot be performed because the pearl pigment sediments during centrifugal defoaming.

Viscosity change test: Viscosity is measured immediately after ink preparation and after aging. -Measurement conditions: E-type viscometer, 1 rpm, 25 ° C (unit: poise). -Aging condition: Put in a glass screw cap bottle and leave in a constant temperature room at 50 ° C for 1 month.

Writing test: The handwriting immediately after preparation of the writing sample and the handwriting after the passage of time are observed. -Writing sample: 0.8 g was directly filled in a transparent ink containing tube made of a polypropylene hollow shaft cylinder having a ball-point pen tip connected at one end, and a backflow preventive member was placed on top of the transparent ink containing 0.1 g.
After filling with g, the bubbles were centrifugally degassed. However, the ink obtained in Example 4 was used for the stainless ballpoint pen tip (ball material:
0.8 g of an ink containing tube made of a stainless steel barrel having one end connected with (a cemented carbide) is filled with a pressure of 3.
0 kg / cm ² was applied.・ Writing paper: Fine paper (JIS 3201 Writing paper A) ・ Aging condition: Leave the pen tip facing down in a thermostatic chamber at 50 ° C for 1 month. Evaluation ○ ・ ・ ・ Writing is good △ ・ ・ ・ Smear occurs × ・ ・ ・ Writing is not possible

Sedimentation degree test: measuring the supernatant of the ink after aging. Sample: 0.8 g of ink in a transparent ink containing tube (inner diameter 3.0 mm) made of polypropylene hollow shaft cylinder.
Filled. -Aging condition: left in a thermostatic chamber at 50 ° C for 1 month. Evaluation Clearance length / Ink column length (unit: mm)

[0028]

As described above in detail, the water-based metallic luster color ink for ballpoint pens of the present invention gives a clear metallic luster color handwriting and is stable with long-term storage without ink deterioration. It is useful and can sufficiently achieve the intended purpose.

Claims (1)

[Claims] 1. A pearl pigment, a thickening resin, a solvent and at least water, and a viscosity of 10,000 to 150,000 c.
ps (ST rotor of E type viscometer, 1 rpm, 25 ° C.), water-based metallic luster color ink for ballpoint pens.